On 14 October 1654 she married Francesco I d'Este, Duke of Modena and was the mother of Rinaldo d'Este who succeeded his father as Duke of Modena. The couple married in Loreto, Marche at the Basilica della Santa Casa. In many ways the marriage represented a long-overdue truce between the House of Este and the Barberini who had taken sides against each other during the First War of Castro. Francesco had, in fact, fought alongside his father against Taddeo Barberini's troops.