He was born at Gedern Castle, Hesse, the third and last child of Count Hermann zu Stolberg-Wernigerode (1802–1841, himself a son of Henry of Stolberg-Wernigerode) and his wife Countess Emma zu Erbach-Fürstenau (great-granddaughter of George Albert III, Count of Erbach-Fürstenau).

The ancient noble House of Stolberg had been quasi-sovereign rulers of their County of Stolberg-Wernigerode until the German Mediatisation, when they came under the jurisdiction of Prussia in 1815.

In 1867 he was appointed First President (Oberpräsident) of the Prussian Province of Hanover at the instigation of Minister-president Otto von Bismarck.

He also supported Bismarck's Anti-Socialist Laws, however, over time had more and more differences with the Chancellor and finally resigned from office in 1881.

Stolberg remained an active politician, serving as Prussian treasurer and Minister of the Royal House.