This work was painted at the start of Rossetti's affair with Jane Morris, who modelled for the picture.

As he was to do with Beata Beatrix (1870), Rossetti chose a tale by Dante Aligheri (from Purgatorio) to illustrate his love for his model.

The story tells of a woman whose husband imprisoned and later poisoned her:[1] Rossetti wanted the world to believe the fantasy with which he was deluding himself – that William Morris kept Jane against her will.

Amongst other representations of her, Rossetti depicts Jane as Proserpine, Queen Guinevere and Desdemona – all of whom were at the mercy of men.

In Pia de' Tolomei her elongated neck seems almost dislocated, and the whiteness of her skin shines out, defying the viewer to pay attention to any other aspects of the painting.