The college was founded in 1624 by King James I of England and VI of Scotland, using in part the endowment of merchant Thomas Tesdale, and was named after William Herbert, 3rd Earl of Pembroke, Lord Chamberlain and then-Chancellor of the University.

A former Senior President of Tribunals and Lord Justice of Appeal, Sir Ernest Ryder, has held the post of Master of Pembroke since 2020.

However, in 1623, this money was augmented by the Reverend Richard Wightwick, parish priest of East Ilsley, and used instead for the conversion of Broadgates Hall into Pembroke College.

Pembroke alumnus Dr. Damon Wells was a significant benefactor of the college over many years: he funded the restoration of the Chapel in 1972 and again in the 1990s and provided ongoing support to the Chaplaincy and History Fellowship.

[12] In April 2013 HRH The Duke of Kent officially opened a new quadrangle named after the lead donor Chris Rokos[15] The new buildings include a 170-seat multi-purpose auditorium, a new café, art gallery, and teaching and function rooms.

The development is physically joined to the college's existing city-centre site via a new bridge crossing Brewer Street and the original medieval city wall, and 'landing' in the old Fellows' Garden adjacent to Chapel Quad.

[21] In March 2002 two Pembroke fellows resigned after allegations that they had offered a place to the fictional child of an undercover reporter in return for a donation to the college library; a journalist had taped a conversation where he posed as the father of a fictitious son.

[34] In more recent years, Danielle Ivory,[35] award winning journalist at the New York Times; Pete Buttigieg, US presidential candidate; and military historian Jonathan Fennell,[36] have completed graduate degrees at Pembroke.

Thomas Randolph, principal of Pembroke's precursor mediaeval hall, Broadgates, served as ambassador for Elizabeth I to Scotland from 1559, where he gained the friendship of Mary, Queen of Scots, until he was accused of supporting the rebellion of James Stuart.

[38] More recently, John, Baron Kerr of Kinlochard, served as HM Ambassador to the United States from 1995 to 1997, before being appointed Head of the British Foreign and Commonwealth Office.

Peter, Baron Ricketts was Head of the Foreign and Commonwealth Office from 2006 until 2010, before serving as British Ambassador to France for six years until his retirement in 2016.

Sir Ernest Ryder, a former Lord Justice of Appeal, succeeded Dame Lynne Brindley as Master of Pembroke College on 1 July 2020.