Duke Eugen was born at Bückeburg, Schaumburg-Lippe, second child and first son of Duke Eugen of Württemberg (1820–1875) and Princess Mathilde of Waldeck and Pyrmont) and his wife, Princess Mathilde of Schaumburg-Lippe (1818–1891).

Back in September 1866 after the war, until 1870 he leave the military service to continue his studies, he lived for one period in Paris.

Together with his uncle, Duke William of Württemberg, he undertook from July 1868 to January 1869 a trip to the United States.

During the Franco-Prussian War of 1870-71, he fought as a lieutenant in the Battles of Mezieres, Chevilly, Mont Mesly and Villiers.

On 8 May 1874, in Stuttgart, he married Vera (1854–1912), daughter of Grand Duke Konstantin Nikolayevich of Russia and Princess Alexandra of Saxe-Altenburg.