Duval College slowly grew over a ten year period. In 1949 weatherboard 'Huts A and B' were built as the first student accommodation on campus for women residents. By 1957 a further five huts had been built and by 1959 the last two huts were completed with housing for 117 women residents. In December 1959 the University Council resolved that the 'Hill Residences' form the second women's college (Mary White College was completed in 1958) and was formally named Duval College. Miss G.A. Rennison held the position of Principal from 1959 to 1962. In 1965 the current Duval College residential buildings were completed, housing a total of 200 students.
After a period serving the college as Bursar, Mrs Edwina Ridgway was appointed college Principal in 1978 and has held this position since.
The college continued developing with new teaching facilities completed in 1978 with further extension in 1985. In 1986, the Tanderra extension was completed supporting the recreational and cultural pursuits of the resident body.
Over the years various innovations in the development of the college have kept pace with changing needs and student services. These have included a fully operational fine dining restaurant, Conference Centre, Thesis Room, computing centre and gymnasium.
To support the long term commitment by the College to charity fundraising and student development, the College maintains an investment in kayaks carried by a specially fitted trailer, for use in recreational paddling as well as east coast Marathons, including the annual Hawkesbury Canoe Classic.