Pedro de Toledo Osorio y Colonna or Pedro Álvarez de Toledo Osorio, 5th Marquess of Villafranca del Bierzo, (Naples, 6 September 1546 – 17 July 1627), Governor of the Duchy of Milan, 1616–1618, Prince of Montalbano, 2nd Duke of Fernandina was a Spanish-Italian nobleman and a Grandee of Spain.

He was the son of García de Toledo Osorio, 4th Marquess of Villafranca, and Vittoria Colonna di Paliano.

In June 1585 Pedro was appointed captain general of the galleys of the Kingdom of Naples and fought the Ottoman corsairs in the Mediterranean Sea.

The expulsion of the Spanish moriscos since 1610 increased the Ottoman naval attacks in the West Mediterranean, especially when young Ahmed I became Sultan.

Between 1616 and 1618, he was Governor of the Duchy of Milan, where he led the Spanish Army in the second phase of the War of the Montferrat Succession against Savoy and France.