La Rochefoucauld received a scanty formal education. He was married at the age of fifteen to Andrée de Vivonne, a cousin of Catherine de Vivonne, the future marquise de Rambouillet. He joined the army the following year and almost immediately established himself as a public figure. He took part in the annual campaigns and displayed the utmost bravery, though this was never formally recognised. Then he met Madame de Chevreuse, the first of three celebrated women who influenced his life.

Under the patronage of Madame de Chevreuse, he joined the service of Queen Anne of Austria, and in one of her quarrels with Cardinal Richelieu and her husband, a wild scheme was apparently conceived by which Marcillac was to carry her off to Brussels on a pillion. Similar cabals against Richelieu once got Marcillac sentenced to eight days in the Bastille, and he was occasionally "exiled"; that is, ordered to retire to his father's estates. After Richelieu's death in 1642, much ambition arose among the French nobles to fill the power vacuum. Marcillac became one of the so-called important ones, and took an active role in pairing the queen and Condé in league together against Gaston, Duke of Orleans. But the growing reputation of Mazarin impeded his ambition, and his 1645 liaison with the beautiful Duchess of Longueville made him irrevocably a Frondeur. He was a conspicuous figure in the siege of Paris, fought desperately in many of the engagements which were constantly taking place, and was severely wounded at the siege of Mardyke.

In the second Fronde, Marcillac allied himself with Condé. At his own father's funeral in 1650 he attempted to recruit the attending nobility of the province to attack the royalist garrison of Saumur. The attempt was not successful. The cabals and negotiations of the later Fronde were tortuous; it is said that Marcillac was always brave and generally unlucky. In the battle of the Faubourg Saint - Antoine, in 1652, he was shot through the head, and it was feared that he would lose the sight of both eyes. It took him nearly a year to recover.

For some years thereafter, he retired to his country estate of Verteuil with nothing to show for his twenty years' of fighting and intrigue except impaired health, a seriously reduced fortune, and cause for bearing a grudge against almost every party and man of importance in the country. He was fortunate enough, thanks chiefly to the fidelity of Gourville, who had been in his service, and who, passing into the service of Mazarin and of Condé, had acquired both wealth and influence, to be able to restore, in some measure, his fortune. He did not, however, return to court life until just before Mazarin's death, when Louis XIV was about to assume absolute power, and the aristocratic anarchy of the Fronde was over. He wrote his memoirs during this time, as did almost all of his prominent contemporaries.

Somewhat earlier, La Rochefoucauld had taken his place in the salon of Madeleine de Souvré, marquise de Sablé, a member of the Marquise de Rambouillet côterie, and the founder of a kind of successor to it, whose special literary work was the writing of Sentences and Maximes. In 1662, the Elseviers surreptitiously published what purported to be his memoirs, which brought him both trouble and fame, more of the former than the latter. Many of his old friends were deeply wounded, and he hastened to deny the memoirs' authenticity, a denial which was not generally believed. Three years later, in 1665, he anonymously published the Maximes, which established his position among the men of letters of the time. At about the same date, his friendship with Marie - Madeleine Pioche de La Vergne, Comtesse de La Fayette, began, which lasted for the rest of his life. The glimpses which we have of him henceforward are chiefly from the letters of Madame de Sévigné, and though they show him suffering agonies from gout, are on the whole pleasant ones.

He had a circle of devoted friends and was recognized as a top-ranking moralist and man of letters. His son, the Prince de Marcillac, to whom he gave his titles and honours in 1671, enjoyed a considerable position at court. But above all La Rochefoucauld was recognized by his contemporaries from the king downward as an exemplar of the older noblesse, the nobility that existed under the great monarch before the brilliance of his reign faded. This reputation he has retained to the present day.

La Rochefoucauld's ethical views have given rise to some prejudice against him, but his character seems to have been respectable and even likable. Like most of his contemporaries, he saw politics as a chessboard where most of the population were moved merely as pawns, yet he appears to have been unusually scrupulous in his personal conduct, and his lack of success in the aristocratic struggles arose more from this than from anything else. He may have been one of those men whose keenness of intellect, together with their apprehension of both sides of a conflict, might cause them to be described as "irresolute," but there is no ground for regarding the Maximes as the spiteful outpourings of a failure. Neither did the gently cynical view of life they contain apparently impede his enjoyment of company, including his romantic engagements.

He died in Paris on the 17th of March 1680 of gout.

His importance as a social and historical figure is perhaps overshadowed by his importance to literature. His literary work consists of three parts — his Memoirs, the Maximes and his letters.

The Memoirs exceed all others of their time in literary merit, in interest, and in value, exceeding even those of Retz, between whom and La Rochefoucauld there was a strange mixture of enmity and esteem which resulted in a couple of most characteristic "portraits", yet their history of publishment is a strange one. A pirated edition appeared in Holland and despite the author's protest, continued to be reprinted for some thirty years. Typical of the habitual plagiarism of the day, this work has now been proved to be a mere cento of the work of half a dozen men, scarcely a third of it being La Rochefoucauld's. Some years after La Rochefoucauld's death a new recension appeared, with some errors corrected, but still largely adulterated, and this work went unchallenged for more than a century. Only in 1817 did anything like a genuine (though by no means perfect) edition appear.

The Maximes, however, had no such fate. The author made frequent alterations and additions to them during his life and a few were added after his death. It is usual now to publish them in their totality of approximately seven hundred. The majority consist of just two or three lines, and hardly any exceed half a page. The view of human conduct they describe has been summed up by the words "everything is reducible to the motive of self-interest" but this is somewhat unfair. La Rochefoucauld reflects on the conduct and motives of himself and his fellows. His Maximes represent the mature thoughts of a man deeply versed in the business and pleasures of the world, and possessed of an extraordinarily fine and acute intellect. There is no spite in them, nor is there any boasting or gloating, but their literary value even surpasses this ethical soundness. For brevity, clarity, fullness of meaning and point, La Rochefoucauld has no rival. His Maximes never become platitudes, nor yet dark sayings. He has packed them so full of meaning that it would be impossible to pack them closer. He has sharpened their point to the utmost, yet there is no loss of substance. The comparison which occurs most frequently, and which is perhaps the most just, is that of a bronze sculpture — a completed work, yet one whose workmanship is not over-detailed. Their sentiment is never merely hard, as the sentimentalists pretend, but has a vein of melancholic poetry running through it which reflects La Rochefoucauld's appreciation of the romances of chivalry. The maxims are never singular; each could give rise to a whole sermon of application and corollary. And the language in which they are written is French, still at the peak of its power, chastened, but as yet not emasculated by the reforming influences of the 18th century.

His letters number more than one hundred, and they are of both biographical and literary value.

La Rochefoucauld's theories on human nature concern self - interest and self - love, the passions and the emotions, love, conversation and sincerity (and the lack of it).

Nearly all the great French critics of the 19th century wrote to some extent about La Rochefoucauld.

For a recent assessment of La Rochefoucauld's thought and his place in modern culture see John Farrell, Paranoia and Modernity: Cervantes to Rousseau. Philosopher Friedrich Nietzsche had a great admiration for La Rochefoucauld and was influenced not only by his ethical stance, but also his writing style.

The editions of La Rochefoucauld's Maximes (as the full title runs, Réflexions ou sentences et maximes morales) published in his lifetime bear the dates 1665 (editio princeps), 1666, 1671, 1675, 1678. Previous editions were superseded by that of Jean Désiré Louis Gilbert and Jules Gourdault (1868 – 1883), in the series Grands Écrivains de la France, 3 vols. The handsomest separate edition of the Maximes is the so-called Édition des bibliophiles (1870). The English version is The Moral Maxims and Reflections of the Duke De La Rochefoucauld by George H. Powell (1903).