Rooke first worked in an army agent’s office before attending evening classes in art and became a student at the Royal Academy in 1868. The following year he was employed by the designer William Morris’s firm and became an assistant and close friend of the artist Edward Burne-Jones, for whom he worked until Burne-Jones' death.
Rooke enjoyed also success as an artist in his own right. He painted large biblical scenes in a style influenced by Burne-Jones, the Arts and Crafts movement and Renaissance art, and exhibited at the Royal Academy and other galleries in London. John Ruskin also employed Rooke through the Guild of St George, and for him Rooke worked in a different style, drawing in watercolours and painting from life, in particualr landscapes and architectural copies.
Later, Rooke painted records of architecture for the ‘Society for the Preservation of Pictorial Records of Ancient Works of Art’ which were similar in concept to works in the Ruskin Collection. He continued to paint until he was 98 years old.