He was born as the third son of Duke Karl Alexander and his wife, Princess Maria Augusta of Thurn and Taxis (11 August 1706 – 1 February 1756).

Her paternal grandparents were Edward Fortunatus, Margrave of Baden-Rodemachern (1565–1600) and Baroness Maria of Eicken (1569-1636).

Edward was a son of Christopher II, Margrave of Baden-Rodemachern (1537–1575) and Princess Cecilia of Sweden (1540–1627).

He married (initially morganatically) Countess Sophie Albertine von Beichlingen (15 December 1728 – 10 May 1807), a daughter of August Gottfried Dietrich, Count of Beichlingen (1703–1769) and his wife, Sophie Helene, Baroness of Stöcken (1710–1738).

Louis and Sophie had three daughters: He succeeded his brother Karl Eugen as Duke of Württemberg in 1793, and reigned until his own death in 1795, when he was succeeded by his younger brother Frederick Eugen.