The miniature of Grand Duchess Catherine Pavlovna, later Queen of Württemberg, is among the finest of Alois Gustav Rockstuhl's portraits. It portrays Catherine at around 4 years of age and is one of the few miniatures of children in the museum's collection. This work was painted several decades after Catherine's death and is based on a large-scale, late 18th-century oil painting by Petr Zharkov. A member of Catherine's family likely commissioned the portrait from Rockstuhl as a memento. Zharkov also painted Catherine's three sisters in similar poses, and although Rockstuhl probably reproduced these portraits in miniature as well, the location of each is currently unknown.

The star of the Order of Saint Catherine is partially hidden beneath the delicate white ruffled neckline of her dress. The only order available to women in imperial Russia, it established Catherine as a member of the royal family while also referring to her saintly namesake. Catherine grew to be an intelligent and charming woman, deeply loved by her older brother Tsar Alexander I and famous for rejecting the marriage proposal of Napoleon Bonaparte. Catherine married twice, gaining the title Queen of Württemberg through her second marriage to her cousin Prince William of Württemberg. She died tragically of erysipelas complicated by pneumonia in 1819 at the age of 31, leaving behind four children and a reputation as a charitable and kind ruler.