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Born in Warri, Alele-Williams attended Government School, Warri, and Queen's College, Lagos. She attended the University College (now the University of Ibadan), the University of Vermont (U.S.). and the University of Chicago (U.S.).
Her teaching career started at Queen’s School, Ede Osun State, where she was mathematics master from 1954 until 1957. She left for the University of Vermont to become a graduate assistant and later assistant professor. Between 1963 and '65, Alele-Williams was a post doctoral research fellow, department (and institute) of Education, University of Ibadan from where she was appointed a professor of mathematics at the University of Lagos in 1976.
By serving in various committees and boards, Alele-Williams had made useful contributions in the development of education in Nigeria. She was chairman of the curriculum review committee, former Bendel State 1973-1979. From 1979-1985, she served as chairman of the Lagos State Curriculum Review Committee and Lagos State Examinations Boards.
Alele-Williams was a member of governing council, UNESCO Institute of Education. She is also a consultant to UNESCO and Institute of International Education Planning. For a decade (1963–73) she was a member of the African Mathematics Programme, located in Newton, Massachusetts, United States. She was also vice-president of the World Organisation for Early Childhood Education and later president of the Nigerian chapter. Alele-Williams has published a book titled Modern Mathematics Handbook for Teachers. She has 5 children and 9 grandchildren.
After serving as the Vice-Chancellor of the University of Benin, she joined the board of directors of Chevron-Texaco Nigeria.
- Nkechi Nwankwo (2006), Women Leadership in Nigeria: Stories of Four Women Role Models, Lagos: Deutchetz Publishers. Review by Theresa Onwughalu in the Daily Sun, July 25, 2006.
- "Biographical sketches of famous African mathematicians: Grace Alele Williams", AMUCHMA Newsletter (African Mathematical Union, Commission on the History of Mathematics in Africa) 12.
- Larry Riddle, "Grace Alele Williams", Biographies of Women Mathematicians, Agnes Scott College.