Frederick began his military career in the Army of Württemberg (German: Württembergische Armee) where by the age of 15, he had reached the rank of Rittmeister 2nd class.

[1] In the Austro-Prussian War against Prussia, Frederick held no field command, but instead served as a liaison officer at the headquarters of the Austrian Feldzeugmeister.

[2] Because of his position as a Prince of Württemberg, Frederick held a served as a member of the Württembergian Chamber of Lords (German: Württembergischen Kammer der Standesherren) at which he regularly attended legislative sessions.

[1] During this time, Frederick resided mainly at Ludwigsburg Palace near Stuttgart and at the hunting lodge Schloss Katharinenhof in Oppenweiler.

[1] Sophie, Queen of the Netherlands wrote of her cousin Frederick to Lady Malet upon learning of his death.