A scholar of Trinity College, Cambridge, Colvin became a fellow of his college in 1868. In 1873 he was Slade Professor of Fine Art, and was appointed in the next year to the directorship of the Fitzwilliam Museum. He wrote numerous articles on fine arts subjects for the ninth edition of the Encyclopædia Britannica. In 1878, 114 Old Master engravings, which Colvin had purchased for the museum from London art dealer A. W. Thibaudeau, were stolen by a hansom cab driver. Although the driver was tracked down and charged, the engravings were never recovered and Colvin was required to cover their cost. Colvin paid the £1,537 10s to Thibaudeau from his own salary in instalments for many years, having initially to borrow £400 from Robert Louis Stevenson; a debt which he was still repaying to his friend in 1884. In 1884 he moved to London on his appointment as keeper of prints and drawings in the British Museum. His chief publications are lives of Walter Savage Landor and Keats, in the English Men of Letters series; editions of the letters of Keats ; A Florentine Picture-Chronicle, and Early History of Engraving in England. In the field both of art and of literature, Colvin's fine taste, wide knowledge and high ideals made his authority and influence extend far beyond his published work.
Frances Jane Sitwell and Robert Louis Stevenson
In the early 1870s Colvin met the woman who was to become his wife, many decades later. Frances Jane, née Fetherstonhaugh, was married to Rev. Albert Hurt Sitwell, a Church of England vicar. The Sitwells had two sons: one died as a child, and one lived to early adulthood, Frances Albert 'Bertie' Sitwell. Their marriage was unhappy, so they lived apart and she earned her living as an essayist. In late summer 1873, Colvin became friends with Robert Louis Stevenson, then a young man and an unpublished author. Soon after their first meeting he had placed Stevenson's first paid contribution, an essay, "Roads", in The Portfolio. Both men were attracted to Sitwell; Stevenson wrote to her for years. Despite or because of this attraction, the men remained firm friends. Stevenson dedicated Travels with a Donkey in the Cévennes to Colvin, who became his literary adviser. Colvin was a significant editor of Stevenson's, preparing the Edinburgh edition of his works ; the Vailima Letters, which Stevenson chiefly addressed to him; and the posthumous collection of Letters. These publications made Colvin an authority on Stevenson's life and work. He also wrote the sketch of Stevenson for the Dictionary of National Biography, and was to have written an authoritative Life, intended for publication simultaneously with the Letters, but was obliged to relinquish the task to Graham Balfour. Sitwell and Colvin married on 7 July 1903, following the death of her husband and his mother. They had 20 years of married life, before she died on 1 August 1924. The couple were the subject of a 1928 biography by E. V. Lucas. According to the literary critic R. L. Calder, the Colvins were models for Mr and Mrs Barton Trafford in W. Somerset Maugham's 1930 Cakes and Ale.