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Queen's is distinguished from all but a handful of other Canadian universities by the fact that its most powerful official is a "Principal," not a "President." This reflects the University's Scottish heritage: the University's founders chose this more modest title, which emphasizes the Principal's role as an academic among academics, in imitation of Edinburgh University, their model for Queen's. At first, the Principal of Queen's had to be a Presbyterian minister and always held the concurrent position of Primarius Professor of Theology; that requirement formally ended in 1912, when Queen's separated from the Presbyterian Church. Still, the old tradition proved persistent; the string of Principals who were ministers was not broken until 1929. Since then the office has been held by a geologist, a classicist, two political scientists, three economists and a biologist.

Throughout, as chief academic and executive officer, the Principal has remained the University's most important official. The Principal is accountable to the Board of Trustees for the management of the University (for administration, budget, and staffing, for example), and to the Senate for the implementation of academic policies. The Principal chairs the Senate and serves as the link between Queen's two principal governing bodies. The administrative responsibilities that accompany the office are considerable: the Principal is responsible for setting the overall budget allocations for each faculty and school, in consultation with the Vice-Principals and the Deans; the Principal as well must approve every academic appointment, promotion, or award of tenure or leave, after receiving recommendations from the Vice-Principal (Academic) and relevant dean and department head.

The Principal also plays a major role in policy-making by formulating proposals for the academic and physical development of the University for consideration by the Board and the Senate. An important role in formulating policies is also played by advisory committees under the Principal's authority. In recent years these have included the committees advising on the status of women, gender issues, race relations, alcohol awareness, disabilities, resource issues and corporate involvement. The Principal, or his delegate, is a member of most Board and Senate committees, and the Principal chairs, the Senate Agenda Committee, and the Senate Committee on Honorary Degrees, as well as the Executive Committee of the University Council and all committees to select Vice-Principals and Deans. The Principal is also responsible for representing the university on such external bodies as the Council of Ontario Universities (COU) and the Association of Universities and Colleges of Canada (AUCC).

Since 1974, Principals have been appointed for five-year terms, renewable subject to review. The formal authority for the appointment of the Principal rests under the Royal Charter with the Board of Trustees. Recent Principals have been selected by a joint committee of Trustees and Senators including , faculty, students, alumni, trustees and staff. There has been some confusion about the official numbering of Queen's Principals because the University was led by an acting principal for four years in the 1850s. The current convention is to include that Acting Principal in the official count.

Principals since 1841:
The Rev Thomas Liddell (1841-1846)
The Rev John Machar (1846-1853)
The Rev James George (acting Principal 1853-1857)
The Rev John Cook (1857-1859)
The Rev William Leitch (1859-1864)
The Rev William Snodgrass (1864-1877)
The Rev George Monro Grant (1877-1902)
The Rev Daniel Miner Gordon (1902-1916)
The Rev Robert Bruce Taylor (1917-1929)
Sir William Hamilton Fyfe (1930-1936)
Robert Charles Wallace (1936-1951)
William Archibald Mackintosh (1951-1961)
James Alexander Corry (1961-1968)
John James Deutsch (1968-1974)
Ronald Lampman Watts (1974-1984)
David Chadwick Smith (1984-1994)
William Claude Leggett (1994-2004)
Karen R. Hitchcock (2004-2008)
Thomas R. Williams (2008-2009)
Daniel Robert Woolf (2009 to present)