Born November 21, 1836, in New York state, George Williamson Smith had a varied career, beginning with his graduation from Hobart College in 1857. He became an Episcopal deacon in 1860. Between 1861 and his inauguration as Trinity's President, he served as clerk in the United States Navy, Professor of Mathematics at the Naval War College in Newport, chaplain at the United States Naval Academy, chaplain on the U.S.S. Franklin, and rector of Grace Church on Long Island. On May 17, 1883, when he accepted the presidential position at Trinity, Smith had been rector of the Church of the Redeemer in Brooklyn, New York for about three years.

Arriving in 1883, President Smith had become so popular in just two years that students and trustees begged him to remain at Trinity, rather than take the Bishopric of Easton, Maryland, when he was offered that post in November 1885. He graciously complied. In staying on, he was able to oversee a modernization of administration that saw advances in curriculum, student societies, rising standards in masters degrees, the hiring of a full-time librarian, and alumni enthusiasm. Electric lights and a large flagpole were installed. By 1888, the undergraduates numbered over one hundred, a new record high. While he was not alone responsible for all these changes, Smith's warmth contributed to the general good feeling. In particular, Smith was successful at giving weight to funding new building projects on campus through annual donations and targeted giving by the alumni. Bringing back Sunday church services, he was confident that religion should not be diminished in its influence at the College.

Also, Smith's tenure as President of Trinity College coincided with the end of the era in which the leadership of the College was divided between the Office of the President and the presiding Chancellor, then long-serving Bishop (and former Trinity President) John Williams. In November 1888, Smith was elected Bishop-Coadjutor of the Diocese of Northern Ohio. Rather than declining quickly, he waited until he could effect (or negotiate) two changes to the College's charter, thereby eliminating the office of the Chancellor and making the President of the College simultaneously President of the Board of Trustees of Trinity. Both proposals were approved by the state legislature on February 20, 1889. Additionally, he was adamant about removing Trinity's president from the Board of Trustees of the Berkeley Divinity School, a seminary in New Haven, Connecticut. By 1896, he had forced the charter of Berkeley to be modified. He was elected one of the vice presidents of the Association for Promoting the Interest of the Protestant Episcopal Schools, Colleges, and Seminaries, an indication that his desire to separate the College and church was not tied to a desire to downplay religious instruction.

Unfortunately, Smith's inability to recruit new students and the problem of declining academic quality among the undergraduates led to his undoing as president. He had to dial back his aspirations, restating “the old idea…[to] never want more than 100 students” in attendance at Trinity. The finances of the College were in shambles by 1901, when a deficit of over $60,000 was owed. In response, Smith talked about winning state support for the College, or offering free student scholarships. In response to these unfathomable ideas, the Trinity Board of Fellows asked for Smith's removal.

The Board of Trustees did afford President Smith the chance to resign with dignity, which he did on June 5, 1903. The Trustees even allowed him to remain “on leave” until June 30, 1904, when his resignation would take effect. They also voted him (at age 67) an annual lifetime pension of $3,000 and honored him with the title “President and Professor of Metphysics Emeritus.”