Princess Charlotte (1766-1828) was the eldest daughter and fourth child of George III (1738–1820) and Queen Charlotte (1744–1818). Like her sisters, Charlotte led a sheltered early life at Windsor Castle. The King was very attached to his daughters and reluctant to let them marry and leave home. Princess Charlotte was the first of the sisters to marry. In 1797, aged 31, she became the wife of Prince Friedrich of Württemberg (1754–1816), a 42-year-old widower. When he died in 1816, Charlotte remained in Württemberg where she died in 1828.

The identity of the artist is unknown but the portrait may be a copy after a painting by Edward Miles, possibly by Ann Mee, who made a number of copies after Miles' miniatures.