Until the twentieth century, this painting was thought to be a portrait of Mary, Queen of Scots; however, it has since been tentatively identified as Mariana of Austria (1634-1696), second wife of Philip IV of Spain (1605-1665).

The painting does not strongly resemble extant portraits of Mary, Queen of Scots nor Mariana of Austria. Both were painted in in mourning dress during widowhood; however, in Francois Clouet's 1560 portrait of Mary, Queen of Scots, painted after the loss of three members of her immediate family, she wears the then traditional white mourning — en deuil blanc. There are various versions of Clouet's portrait, for which a red and black chalk study survives in Paris (Bibliothèque Nationale); however, all show the Queen of Scots in white, rather than black. Similarly, Juan Bautista Martínez del Mazo's 1666 portrait of Queen Mariana of Spain in Mourning (National Gallery, London, NG2926) and its known copies shows the Queen in traditional Spanish court morning, wearing a black and white habit.

It is not possible to definitively identify this painting in the Royal Collection prior to January 1863, when it was recorded at Windsor Castle. However, a notation made at that time, referring to the painting as 'Crown Property' indicates that the painting was not purchased by Queen Victoria and was in the Royal Collection before her accession in 1837. It has been tentatively associated with the painting recorded in the records of the Commonwealth Sale as 'A woman in black with a cross in her hand', sold to Mr De Criz, 18 November 1651 for £6. However, the general appearance of the picture, particularly the rather soft, pretty, treatment on the sitter's features, suggests that the picture may be a later work.

A version of the portrait is believed to have at one time been in the collection at Murthly Castle, Scotland.