Born in 1790 near Carlisle, Pennsylvania George Junkin graduated from Jefferson College in 1813. He entered the Theological Seminary of the Associate Reformed Church in New York City and was licensed to preach by the Presbytery of Monongahela in 1816. Junkin was ordained by the Presbytery of Philadelphia in 1818. He served as pastor of the Associated Reformed Church of Milton, Pennsylvania from 1819 to 1822.

In 1830, Junkin became Principal of the Manual Labor Academy in Germantown, Pennsylvania. Two years later he became the first President of Lafayette College in Easton, Pennsylvania. In 1841 he accepted the Presidency of Miami University in Oxford, Ohio remaining there for three stormy years, before returning to Easton.

Junkin served as the Moderator of the General Assembly of the Presbyterian Church in 1844. In the fall of 1848 he became the President of Washington College (now Washington and Lee University) in Lexington, Virginia where he remained until 1861. He resigned the presidency at the age of 71 and moved to Philadelphia. George Junkin died in Philadelphia in 1868.