In 1862 in Chester's Congregational church, the Rev. Charles S. Hale of Bellows Falls held Prayer Book services. The following spring, six men signed St. Luke's Articles of Association. Three were village residents on Main Street. Despite the competition from three thriving Protestant churches and community hostility toward the Episcopal Church, the founders, with $400 in pledges and a similar amount from the diocese, called the Rev. Alonzo Flanders to be rector.
Merrick Wentworth was named senior warden. Members of his family and that of Frederick Fullerton, his son-in-law, formed a large part of the congregation. Frederick and Philette Wentworth Fullerton donated a building site across the street from their home, and Mr. Wentworth's nephew, Boston architect, P. Wentworth, contributed plans for a Gothic-style frame church. Services were held in the Chester Academy until it was built. The parish had budgeted $4,000 -- a severe miscalculation. After Frederick Fullerton died before he could increase his pledge, his widow contributed the balance needed-- $11,000 was her gift of the total $14,000 cost.
Construction began in 1869, and on May 25, 1871, Bishop William Henry Augustus Bissell consecrated "one of the most beautiful structures in the state." That same year three Fullerton daughters gave the rectory.