In 1942, she was invited by Sir Daryl Lindsay, the newly appointed Director of the National Gallery of Victoria, to deliver a series of lunch time lectures at Melbourne's premier cultural institution. In 1943, Lindsay appointed Hoff as the NGV's Assistant Keeper of Prints and Drawings. She thus became the first woman and first tertiary qualified art historian to work within a state gallery in Australia. Hoff remained at the NGV until her retirement in 1973, becoming Keeper of Prints and Drawings in 1949, and its Deputy Director in 1968. During her tenure at the National Gallery of Victoria, Hoff pioneered the professional cataloguing of the NGV's holdings; produced important and internationally recognised publications and catalogues of its collections; curated numerous important exhibitions; published monographs on Charles Conder, William Blake, Rembrandt, and many others; secured important works by Paul Klee, Marc Chagall, Albrecht Dürer, Rembrandt, Pablo Picasso, Anthony van Dyck, Giovanni Batista Tiepolo, Salvador Dalí, and innumerable others for the NGV's collection; became Founding Editor of the "Art Bulletin of Victoria"; and published extensively in Australian and International art journals. An excellent source on Ursula Hoff’s early years and her work at the National Gallery of Victoria is Sheridan Palmer’s "Centre of the Periphery: Three European Art Historians in Melbourne" (Nth Melbourne, Vic: Australian Scholarly Publishing, 2008). In 1975, Ursula Hoff was appointed Advisor to the Felton Bequest and moved to London. Over her tenure as the London Advisor, she secured many outstanding works for the National Gallery of Victoria, including Francisco de Goya, Robert Rauschenberg, Bridget Riley, François Boucher, Canaletto, Pierre-Auguste Renoir, and an important suite of 16th- and 17th-century Indian Mughal miniatures. She continued travelling extensively to research the NGV’s collection; assist with the loan exhibition of masterpieces from the State Hermitage, Leningrad, USSR (now St Petersburg, Russia), which toured Australian galleries 1979–80; and continued contributing articles to Australian and International art journals. During her time overseas, she also advised the Everard Studley Miller Bequest, the Art Foundation of Victoria, Art Gallery of South Australia, National Gallery of Australia, as well as a number of high-profile private collections, notably that of James Fairfax. Ursula Hoff retired as London Advisor of the Felton Bequest in April 1983.