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Odhiambo was born in 1966 in Homa Bay to Harrison Odhiambo and Damaris Auma Odhiambo.She is the fourth of eight children. Her father Harrison Odhiambo died in 1973 in a boating accident, a moment that Odhiambo says helped spur her interest in politics.
Millie attended Homa Bay Primary School,St. Francis Girls Secondary School and Limuru Girls High School before she attended the University of Nairobi in 1986. She graduated in 1990 with a Bachelor of Laws degree.She would later study in the United States, Sweden and Italy.
She began her career in the attorney general's office practicing civil litigation before moving on to human rights law, with an emphasis on women and children.[4] In 1999 she served as chairperson of Coalition on Violence Against Women-Kenya and from 2000 to 2008 was the founder and director of the CRADLE Children's Foundation, an organization working to improve children's rights in the legal system.