During the War of the First Coalition he led his troops at Neerwinden and was in command of the successful Siege of Condé in 1793.

In March 1796 Württemberg was promoted to Feldzeugmeister, but after he was defeated by the French at Altenkirchen that June, Archduke Charles, Duke of Teschen removed him from command.

He was promoted to Feldmarschall in 1805 but for the remainder of his military career he held commands in the interior.

On 18 March 1795 in Sondershausen he married Princess Albertine of Schwarzburg-Sondershausen (1771-1829), whom he divorced in 1801.

On 23 February 1817 in Marseille he was married for the second time to Princess Pauline Kunigunde Waldburga of Metternich-Winneburg (1772-1855), elder sister of Austrian statesman and diplomat Klemens von Metternich.