Salomea was born in 1211 to Leszek I the White, High Duke of Poland (Piast dynasty), and his wife Grzymisława of Rus' (Kievan-Rus' royal princess).
At the age of 3 (1214), Salomea was betrothed to Coloman of Galicia (Hungarian Kálmán) — the younger son of King Andrew II of Hungary and younger brother of St. Elizabeth of Hungary (1207–1231, sister-in-law of Salomea). The marriage was a dynastic settlement of the contested Galician-Volhynian succession, in which the Hungarian and Polish crowns shared the contested Ruthenian territory.
Salomea and Coloman were crowned King and Queen of Galicia in 1219 — under the Hungarian-Polish shared suzerainty. Salomea became the first recorded medieval Hungarian queen to publicly wear the royal crown.
The royal marriage remained unconsummated by mutual agreement (in the medieval Catholic tradition of virginity-in-marriage that had been established by Sts. Henry II and Cunigunde of Germany, Edward the Confessor and Edith of Wessex, and other medieval Catholic royal couples).
In 1241, King Coloman died at the Battle of Mohi in April 1241 — the catastrophic Mongol invasion of Hungary that had destroyed the Hungarian royal army. Salomea survived and returned to Poland.
In 1245, Salomea undertook the Poor Clare monastic vocation at the Poor Clare monastery at Zawichost (later transferred to Skała and then to Kraków) — becoming the foundress of the Polish Poor Clare tradition. She served as abbess and established the Polish Poor Clare institutional network.
Her sister-in-law St. Kinga of Poland (1234–1292, wife of Bolesław V the Chaste, younger brother of Salomea) followed Salomea into the Poor Clare life (after her widowhood in 1279); the other sister-in-law Bl. Yolanda of Poland (Jolenta, 1235–1298, Kinga's younger sister) also followed the Poor Clare vocation. The three Polish royal Poor Clare saints (Salomea, Kinga, Yolanda) institutionally established the Polish Poor Clare tradition of the royal-Piast-dynasty women's-monastic culture that would extend through the medieval Polish Catholic centuries.
Salomea died at Skała on November 17, 1268.