He was in line for great estates and position as head of the distinguished Herbert family and heir to the earldom of Pembroke, but lived an irregular life in exile after a dissolute youth.

Herbert was born on 19 September 1791 at Hill Street, London, the second (but eldest surviving) son of the 11th Earl of Pembroke by his first marriage to his first cousin, Elizabeth (d. 1793), who was the daughter of Topham Beauclerk and the former Lady Diana Spencer, eldest daughter of Charles Spencer, 3rd Duke of Marlborough, and great-great-granddaughter of Charles II.

His bride was a Sicilian princess, Ottavia Spinelli (1779–1857), the recently widowed wife of the (much older) Prince Ercole Branciforte di Butera, and daughter of the Duke of Laurino.

"[citation needed] Herbert owned Lancret's "Dance before a Fountain", previously in the collection of Catherine the Great; it became part of his later estate sale in June 1862.

His frequent trips to London resulted in children by Alexina Sophia Gallot (born London 7 March 1821), daughter of John and Ann Gallot: In Paris, he formed a relationship with ballet dancer Marie Catherine Caroline (Elisa) Schäffer, who bore him: He died in Paris 25 April 1862,[3] where he is buried in the Père Lachaise Cemetery.