- William Turnbull (1451)
- Andrew de Durisdere (1456)
- John Laing (1474)
- Robert Blackadder (1483)
- James Beaton (1508)
- Gavin Dunbar (1524)
- James Beaton II (1551–1560)
- John Porterfield (1571)
- James Boyd (1572)
- Robert Montgomery (1581)
- William Erskine (1585)
- Walter Stewart, 1st Lord Blantyre (1587)
- John Spottiswoode (1603)
- James Law (1615)
- Patrick Lindsay (1633)
- James Hamilton, 3rd Marquess of Hamilton (1642)
- John Thurloe (1658)
- William Cunningham, 9th Earl of Glencairn (1660)
- Andrew Fairfoul (1661)
- Alexander Burnet (1664)
- Robert Leighton (1672)
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- Alexander Burnet (1674)
- Arthur Ross (1679)
- Alexander Cairncross (1684)
- John Paterson (1687)
- John Carmichael, 1st Earl of Hyndford (1692)
- James Graham, 1st Duke of Montrose (1714)
- William Graham, 2nd Duke of Montrose (1743)
- James Graham, 3rd Duke of Montrose (1781)
- James Graham, 4th Duke of Montrose (1837)
- Sir William Stirling-Maxwell of Pollock (1875)
- Walter Montagu-Douglas-Scott, 5th Duke of Buccleuch (1878)
- John Hamilton Dalrymple, 10th Earl of Stair (1884)
- William Thomson, 1st Baron Kelvin (1904) *
- Archibald Primrose, 5th Earl of Rosebery (1908)
- Sir Donald MacAlister, 1st Baronet (1929)
- Sir Daniel Macaulay Stevenson (1934–1944)
- Sir John Boyd Orr, 1st Baron Boyd-Orr (1946) *
- Sir Alexander Kirkland Cairncross(1972) *
- Sir William Kerr Fraser (1996) *
- Professor Sir Kenneth Calman (2006) *
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