In 1977, Leo-Rhynie became a lecturer in educational psychology at the UWI School of Education. In 1987, she was appointed executive director of the Institute of Management and Production. She became the regional coordinator of the Centre for Gender and Development Studies in 1992, and in that capacity was co-author of the Jamaican report to the Fourth World Conference on Women in 1995. Leo-Rhynie was appointed deputy principal of the Mona campus in 1996 and principal in 2006 – the first woman to hold either position. She became pro-vice-chancellor and chair of undergraduate studies in 2002, and retired in 2007 as a professor emerita.