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Educated by Samuel Daniel at New College, Oxford, William Herbert succeeded as Earl of Pembroke in 1601.

He was a patron of Ben Johnson and Inigo Jones amongst others, and entertained James I at Wilton House on three occasions. He was a member of the Council of New England and became very interested in Virginia, Northwest passage, Bermuda and East India companies. He was appointed Lord Chamberlain in 1615 and Commissioner of the Great Seal in 1621 although he opposed the foreign policy of James I and Buckingham.

Under Charles I he became Lord Steward in 1626 and was made Chancellor of Oxford University in 1617, Pembroke College being named after him. He presented the Barocci Library to the Bodleian. The first folio of Shakespeare's works published by Thorpe were dedicated to him as Lord Chamberlain and to his brother in 1623.