Browne was born in London, the eldest child of Captain Sylvester John Brown [sic], a shipmaster formerly of the East India Company, and his wife Elizabeth Angell, née Alexander. His mother was his "earliest admirer and most indulgent critic . . . to whom is chiefly due whatever meed of praise my readers may hereafter vouchsafe" (Dedication Old Melbourne Memories). (Thomas added the 'e' to his surname in the 1860s). After his father's barque Proteus had delivered a cargo of convicts in Hobart, the family settled in Sydney in 1831. Sylvester Brown took up whaling and built a stone mansion Enmore which gave its name to the suburb of Sydney. Thomas Browne was sent to W.T. Cape's school at Sydney, and afterwards to Sydney College, when Cape became its headmaster. One of Browne's closest school friends was a son of Colonel John George Nathaniel Gibbes, MLC, the Collector of Customs for New South Wales, and according to the Dulhunty Papers, Browne spent carefree holidays staying with the Gibbes family at their grand waterside residence on Sydney's Point Piper.

When his father moved to Melbourne in 1839, Browne remained at Sydney College as a boarder until 1841 and then was taught by Rev. David Boyd in Melbourne. In 1843, though only 17 years old, Browne took up land near Port Fairy and was there until 1856. He visited England in 1860 and by 1864 had a property in the Riverina. However, bad seasons in 1866 and 1868 compelled Browne to give up squatting, and in 1871 he became a police magistrate and goldfields commissioner. After living in Sydney a short time, in April 1871 he was appointed a police magistrate at Gulgong and gold commissioner in 1872.

Browne was an experienced justice of the peace, having acted as chairman of the bench of justices at Narrandera, but in his first years at Gulgong, then one of the richest and largest goldfields in New South Wales, his ignorance of mining and the complicated regulations drew criticism of his competence as commissioner. He was persistently attacked by the Gulgong Guardian until in 1873 it published an anonymous letter accusing him of bias and corruption. Its editor was thereupon convicted in Sydney of criminal libel and sentenced to six months gaol. The charges against Browne were disproved, and he won favour with the miners by magnanimously interceding with the judge for a light punishment of his libeller. In 1881 Browne was transferred as magistrate and mining warden to Dubbo and to Armidale in 1884. He moved to Albury as chairman of the Land Licensing Board in 1885, serving there as magistrate and warden from 1887 – 1895 until retiring to Melbourne. He died on 11 March 1915 and was buried in Brighton Cemetery.

Browne spent around twenty - five years as a squatter and about the same time as a government official, but his third career as author extended over forty years. In 1865, while recovering from a riding accident, he wrote two articles on pastoral life in Australia for the Cornhill Magazine, and he also began to contribute articles and serial stories to the Australian weeklies. One of these, Ups and Downs: a Story of Australian Life, was published in book form in London in 1878. It was well reviewed but attracted little notice. It was re-issued as The Squatter's Dream in 1890.

In 1884 Old Melbourne Memories, a book of reminiscences of the eighteen - forties was published at Melbourne, "by Rolf Boldrewood, author of My Run Home, The Squatter's Dream and Robbery Under Arms". These had appeared in the Sydney Town and Country Journal and The Sydney Mail, but only The Squatter's Dream had been published in book form and then under the title of Ups and Downs. In 1888 Robbery Under Arms appeared in three volumes and its merits were immediately recognized. Several editions were printed before the close of the century. At the beginning of this novel the narrator, Dick Marsden, is awaiting execution for crimes committed whilst he was a bush ranger. He goes on to tell the story of his life and loves and his association with the notorious Captain Starlight. Some of the events in the book are based on actual incidents carried out by contemporary bush rangers like Daniel Morgan, Ben Hall, Frank Gardiner, James Alpin McPherson and John Gilbert. Robbery under Arms has, remained popular since its first publication in 1888; the novel was filmed in 1907, 1920 and 1957. A television series was made in 1985. The novel has also been serialised on radio in both Australia and Britain.

Browne married Margaret Maria (daughter of W.E. Riley and granddaughter of Alexander Riley) in 1860 who survived him with two sons and five daughters, one of whom, "Rose Boldrewood", published a novel The Complications at Collaroi in 1911. Mrs Browne was the author of The Flower Garden in Australia, published in 1893.

Named in his honour, the 'Rolf Boldrewood Literary Awards' are awarded annually by the Macquarie Regional Library.