 After a childless first marriage to Donna Porzia Guidi dei marchesi di Bagno, he arranged to be married to his relative, Princess Maria Vittoria Gonzaga di Guastalla (1659–1707), the youngest daughter of his cousin, Duke Ferrante III Gonzaga of Guastalla (1618-1678) and Princess Margherita d'Este of Modena (1619-1692) .When Duke Ferrante III of Guastalla died in 1678 without a male heir, Guastalla was ruled by Ferdinando Carlo, Duke of Mantua, who had married Princess Anna Isabella Gonzaga, Duke Ferrante III's oldest daughter.Vincenzo became Duke of Guastalla in 1692.