Williams was born at Deerfield, Massachusetts, the son of Ephraim Williams and Emily (Trowbridge) Williams. He was educated at Harvard and at Trinity College, Hartford, where he graduated in 1835. Although his parents were Unitarian, Williams's time at Harvard convinced him to join the Episcopal faith. He was ordained deacon in 1838 and ordained priest in 1841. Williams held the rectorship of St. George's Church, Schenectady, New York, from 1842 to 1848, after which he became president of Trinity College, and at the same time professor of history and literature.
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