The sitter was the second son of Friedrich II Eugen, Duke of Württemberg and Margravine Sophia Dorothea of Brandenburg-Schwedt. In 1784, he married Maria Czartoryska, with whom he had one child. After their divorce, he married Princess Henriette of Nassau-Weilburg, with whom he had five children. His siblings included Frederick I, the first King of Württemberg and Tsarina Maria Feodorovna of Russia.
In 1804, François Ferrière left London for St Petersburg, where the present miniature was painted. A miniature of Duke Louis's son, Adam, painted by Domenico Bossi in St Petersburg in the same year as the present miniature (1805), was sold Christie's, London, 6 July 2005, lot 150.