His elder brother was Frederick I, the first King of Württemberg, and his sister was the Russian Empress consort, Maria Feodorovna.

[1] His Polish wife, Duchess Maria, divorced him shortly afterward after his treason became public knowledge.

Between 1807 and 1810, Duke Louis employed the composer Carl Maria von Weber as his secretary with no musical duties.

He married on 28 October 1784 Princess Maria Czartoryska (1768–1854), daughter of Prince Adam Kazimierz Czartoryski and his wife, Countess Isabella von Flemming.

They had one child before they divorced in 1793 (Maria initiated the divorce upon the news of his betrayal of Poland): On 28 January 1797 in Hermitage [de], near Bayreuth, Louis Frederick was married to Princess Henriette of Nassau-Weilburg (then of Nassau), daughter of Charles Christian, Duke of Nassau-Weilburg and Princess Carolina of Orange-Nassau.