Jonathan Dickinson, born in 1688 and graduated from Yale College in 1706, was the first president of the College of New Jersey. After becoming the pastor of the Congregational church in Elizabethtown, New Jersey, Dickinson shifted from Congregational to Presbyterian teachings in order to join the Presbytery of Philadelphia. Yet while becoming a leader within the Presbytery and the higher Synod of Philadelphia, Dickinson steadfastly maintained his belief in the freedom of the individual clergy. Having first envisioned an educational institute within the Synod, Dickinson only realized his dream of founding a school to train future Presbyterian ministers and pious laymen when he and others founded the College of New Jersey in 1746. Dickinson died in office in October 1747.

While Jonathan Dickinson bears the distinction of serving as Princeton University's first president, Aaron Burr played a central part in organizing the College after its initial establishment and overseeing its move to Princeton in 1756. Burr was born in Fairfield, Connecticut in c. 1715/1716 and graduated at the head of his Yale College class in 1735. From there he moved to Newark, New Jersey to head both the Presbyterian church and a school in classics. Burr, along with Dickinson and five others, established the College of New Jersey in 1746. In 1748 Burr was named president of the college, though he had filled this office unofficially since Dickinson's death in 1747. During Burr's ten years of service he increased enrollment, raised much-needed funds, presided over the erection of Nassau Hall, and instructed the first classes of students to graduate from the College of New Jersey.

Jonathan Edwards succeeded his son-in- law, Aaron Burr, Sr., to become the third president of the College of New Jersey in September 1757. Edwards studied theology at Yale College, preached in the Presbyterian Church, and is remembered for his belief that only the truly converted should receive Communion, rather than all baptized persons. However, his proposal along these lines led to his dismissal from the Northampton, Massachusetts Presbyterian church in 1750, after which he passed his days serving as a missionary and writing with a passion. Edwards accepted the office of president with some reluctance but continued to preach actively from the College's pulpit. He died in March 1758 after being inoculated for smallpox, just six months into his tenure. His three sons and eight daughters survived him.