Saint Barbara was a third-century Christian martyr imprisoned in a tower and later decapitated by her father, Dioscoro, as punishment for not wanting to marry and refusing to profess paganism. Goya depicts the saint with her various symbols, with a monstrance in her right hand and the palm frond of martyrdom in the left. She wears a crown as she was a princess. The tower is behind her, and a representation of her martyrdom appears at the right edge of the composition.

Goya painted this work shortly after his visit to Italy and it reveals his inspiration by both classical statuary and seventeenth-century classicist Italian painting. This is documented in his Italian notebook, where he studied both the head and the composition.