On 23 August 1800, in Coswig, Frederick married one of his mother's ladies in waiting, Wilhelmine Freiin von Tunderfeld-Rhodis (* 1777; † 1822), daughter of Baron Karl August Wilhelm von Tunderfeld-Rhodis.
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Wilhelm was the son of Duke Wilhelm of Württemberg (1761-1830) and his morganatic wife, Baroness (Freiin) Wilhelmine von Tunderfeldt-Rhodis (1777-1822), whom he married at Coswig on 23 August 1800.