Middlebury College as a junior, earning a bachelor's degree in 1823, reportedly the first African American in the country to do so.
Twilight then taught in Peru, New York while studying theology and was licensed to preach by the Presbyterian Church. In 1829 he was hired as headmaster of the Orleans County Grammar School, later known as Brownington Academy, in Brownington, Vermont. He also served as pastor of the local Congregational church.
Due to disputes with school trustees, Twilight left Brownington in 1847 and taught in Quebec before returning five years later to resume his duties as headmaster until incapacitated by a stroke in 1855. He died June 19, 1857 in Brownington at the age of 61.