Grace Alele williams was born in 1932, Delta State. She attended the government school in Warri, then queens college, Lagos and the University College of Ibadan (now the University of Ibadan).                           
After completing her undergraduate education, she became a master in mathematics at Queen's school, Ede Osun state, from 1954 until 1957. 
Alele Williams obtained her Ph.D in mathematics Education at the University of Chicago in 1963 with a dissertation on "Dynamics of Education in the Birth of a New Nation: Case study of Nigeria". She became the first female professor of mathematics education in 1974. During this time, she also directed the Institute of Education where she introduced programs to benefit teachers as well as being a participant of the African Mathematics Educational Development Center of Newton, Massachusetts, whose goal was to consider changes in mathematics education in Africa.
In 1985, Alele Williams became the first female Vice Chancellor of an African university when she accepted that position at the University of Benin. She remained as Vice Chancellor until 1991.
Professor Alele-Williams also served in various committees and boards, she had made useful contributions in the development of education in Nigeria. 
Alele-Williams was a consultant to UNESCO and the Institute of International Education Planning for a decade (1963–1973). 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. 
After serving as the Vice-Chancellor of the University of Benin, she joined the board of directors of Chevron-Texaco Nigeria. She was also vice-president of the World Organization for Early Childhood Education and later president of the Nigerian chapter. Alele-Williams published a book titled "Modern Mathematics Handbook for Teachers" and numerous articles in national and international academic journals. 
Professor Alele-Williams has won many awards, she was the first Nigerian woman to receive a doctorate degree. Among her honors include Order of the Niger 1987, Fellow of the Mathematical Association of Nigeria and of the Nigerian Academy of Education; Merit Award Winner of Bendel State in Nigeria; and Regional Vice President for Africa of the Third World Organization for Women in Science” (Science in Africa: Women Leading from Strength AAAS, Washington, 1993. It may be added that Professor Williams is also the Chairwoman of AMUCWMA, the African Mathematical Union Commission for Women in Mathematics.
Professor Grace Alele Williams was married to late Professor Babatunde Williams and they are blessed with five children and nine grandchildren.