In 1965, Walker met Melvyn Rosenman Leventhal, a Jewish civil rights lawyer. They were married on March 17, 1967, in New York City. Later that year the couple relocated to Jackson, Mississippi, becoming "the first legally married inter-racial couple in Mississippi". They were harassed and threatened by whites, including the Ku Klux Klan. The couple had a daughter, Rebecca, in 1969. Walker and her husband divorced in 1976.
In the mid-1990s, Walker was involved in a romance with singer-songwriter Tracy Chapman: "It was delicious and lovely and wonderful and I totally enjoyed it and I was completely in love with her but it was not anybody's business but ours."
Walker wrote, "At one point I learned Transcendental Meditation. This was 30-something years ago. It took me back to the way that I naturally was as a child growing up way in the country, rarely seeing people. I was in that state of oneness with creation and it was as if I didn't exist except as a part of everything."
Beauty in Truth, a documentary film about Walker's life directed by Pratibha Parmar, premièred in March 2013.
Walker was also strongly affected by her teen pregnancy and abortion before her senior year of college in the summer of 1965. She became severely depressed and determined to commit suicide. This emotional trauma she experienced pushed her to write her first book of poems Once.