In 1985, however, Hill returned to her alma mater to teach economics, and she began her role as Williams provost in July 1999, holding major financial and academic responsibilities.

In what Hill has called one of the most transformative experiences of her life, she and her family lived from 1994 to 1997 in the Republic of Zambia, where she was the fiscal/trade advisor and then chief-of-party for the Harvard Institute for International Development's Project on Macroeconomic Reform.

Hill succeeded Fergusson on July 1, 2006, and was officially inaugurated in a five-day celebration from October 25–29 that included events for students such as "Cappy and the Chocolate Factory", a party in the Students' Building featuring live entertainment and desserts such as "Cappy candy bars", a cotton candy wall and a chocolate fondue fountain.

Hill highlighted her primary goal as improving affordability and access, and also, as she said at one of her first gatherings with students, to "articulate and build a consensus around a vision of an institution.

Under Hill's leadership, Vassar has also replaced loans with grants in financial aid for low-income families, in further efforts to increase access to higher education.