Born in Warsaw, he was the son of the third Prime Minister of Poland Count Stanisław Kostka Potocki and his wife Aleksandra Lubomirska.

At the end of his life Potocki was involved in a romance with a widow, Aleksandra Stokowska, which he never married.

From 1805 he lived with his wife in the estate in the district of Wilanów, named in 1807 in honour of his daughter Natalia – Natolin (property several times rebuilt by Piotr Aigner, and after the divorce with his first wife in the years 1821–1845 under the supervision of Henryk Marconi).

Potocki was a chamberlain Emperor Napoleon Bonaparte, 1812 has been a member of the Committee set up by him of the Provisional Government of the Grand Duchy of Lithuania.

Potocki did not participate in the November Uprising, nor in any of the sessions of the Sejm, for which in 1831 was expelled from the Senate.