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Masters was born in Cleveland, Ohio, attended the Lawrenceville School and graduated from Hamilton College. He was a member of Alpha Delta Phi, and became a faculty member at Washington University in St. Louis. Masters met Johnson in 1957 when he hired her as a research assistant to undertake a comprehensive study of human sexuality. Masters divorced his first wife to marry Johnson in 1971. They divorced two decades later, largely bringing their joint research and business parternership to an end. Masters died in Tucson, Arizona on February 16, 2001.