After attending high school in Poughkeepsie, Bolin was prevented from enrolling at Vassar College as it did not accept black students at that time. At 16 years old, she enrolled at Wellesley College in Massachusetts where she was one of only two black freshmen. Having been socially rejected by the white students, she and the only other black student decided to live off campus together. A career adviser at Wellesley College tried to discourage her from applying to Yale Law School due to her race and gender. She graduated in 1928 in the top 20 in her class, and enrolled at Yale Law School where she was the only black student, and one of only three women. She became the first black woman to receive a law degree from Yale in 1931 and passed the New York state bar examination in 1932.