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He received a military education in order to become a regular officer. Afterwards, he was commissioned as a lieutenant colonel in the 3rd Cavalry Regiment of Württemberg. The regiment was stationed in Esslingen am Neckar where Alexander von Württemberg stayed in the Obere Palmsche Palais.
Alexander von Württemberg formed a particularly close friendship with Nikolaus Lenau, who shared his dejection and depression. He was married in 1832 to his Hungarian wife, Helene Festetics de Tolna. Together they had two sons and two daughters.
He suffered from chronic headaches and moved to Italy in 1843 in a futile attempt to improve his health. He then moved to Wildbad, Württemberg where he died from a stroke in 1844. His body is interred in the Stiftskirche, Stuttgart.