Proserpine (1874) depicts the goddess as the Empress of the Underworld. According to Greek and Roman mythology, Proserpine was the beautiful daughter of Ceres, the goddess of agriculture. She was abducted by the ruler of the Underworld, Pluto, who brought her to his realm to marry her. Ceres pleaded with Jupiter, the king of gods, for Proserpine's return, and Jupiter agreed under the condition that she had not consumed any of the fruits of the Underworld. However, Proserpine ate six grains of pomegranate, thus she was forced to accept her new role and destiny: her punishment was to spend six months of the year on earth, and six months in the Underworld. In Rossetti's painting, Proserpine is in a gloomy corridor of her palace; she seems pensive and sullen while holding a pomegranate, a symbol of her captivity. Next to her is an incense burner, the attribute of a goddess.

Rossetti, both a poet and a painter, often paired the two arts by creating accompanying poems for his paintings. For Proserpine, Rossetti wrote a sonnet and inscribed it in Italian on the picture and in English on the frame:

Afar away the light that brings cold cheer
Unto this wall, - one instant and no more
Admitted at my distant palace-door.
Afar the flowers of Enna from this drear
Dire fruit, which, tasted once, must thrall me here.
Afar those skies from this Tartarean grey
That chills me: and afar, how far away,
The nights that shall be from the days that were.
Afar from mine own self I seem, and wing
Strange ways in thought, and listen for a sign:
And still some heart unto some soul doth pine,
(Whose sounds mine inner sense in fain to bring,
Continually together murmuring,) -
"Woe's me for thee, unhappy Proserpine!"

The sonnet plays a complementary role, revealing to the viewer the symbolic meaning of the figure in the painting. Through the poem, Rossetti not only draws attention to the myth of Proserpine but also reveals to the viewer the inner thoughts behind her silent expression.

The model in the painting is Jane Morris, the wife of artist William Morris. Jane was one of Rossetti's favorite muses, who embodied the ideal of Pre-Raphaelite beauty. She modeled for many of Rossetti's paintings, including The Day Dream (1880) and Pia de' Tolomei (c.1868). The two also had a romantic relationship, that spanned in various degrees over nearly two decades, until Rossetti died in 1882.

Rossetti painted Proserpine while staying with the couple at Kelmscott. Many have drawn a connection between the myth of Proserpine and the personal life of Jane Morris. By all accounts, Jane was in an unhappy marriage, which was further complicated by her work and relationship with Rossetti. The artist probably viewed Jane as Proserpine, another beauty trapped in a sad situation, unable to free herself from her destiny.
Rossetti often created replicas of his paintings, and Proserpine is one of the most famous examples. A total of eight oil versions were created, this was the seventh, and it was painted for Rossetti's patron, Frederick Leyland. The picture replaced an earlier version that was damaged in transit. Today, Proserpine is part of the collection of Tate Britain, London.