The duke was born July 30, 1838 at Neuilly-sur-Seine, the son of Duke Alexander of Württemberg and Princess Marie d'Orléans. In 1865, he married Archduchess Maria Theresa of Austria, daughter of the Duke of Teschen.
He is survived by his widow and three of their five children: Dukes Albrecht, Robert and Ulrich. Two daughters, Duchess Marie Amelie and Duchess Maria Isabella, the wife of Prince Johann Georg of Saxony, predeceased him.
In 1903, following the death of his cousin, Duke Nicholas, Philipp became the heir presumptive to the throne, a position now fulfilled by his eldest son, Duke Albrecht, who serves as the Commander in Chief of the Germany on the Western front.