Centurione purchased the rights of the title of Prince of Achaea by Ladislaus of Naples in 1404 and was the last ruler of the once Latin Empire not under Byzantine suzerainty.

Centurione was the son of Andronikos Asen Zaccaria and of Catherine Le Maure,[3] daughter of Erard III, baron of Arcadia.

[4] After the death of Prince Pedro San Superan, his widow Maria, sister of Andronikos and aunt of Centurione, took command of the Principality, ruling Achaea in her own right until her children coming to age.

[5] In the past, Pedro had pledged to the King of Naples Ladislaus 3.000 ducats in exchange for the title of the ruler of Morea, an amount of coins he never yielded.

Centurione acted secretly and dispatched a trusted person in Naples to inform Ladislaus that Maria and her children couldn't grant him the money.

Carlo I Tocco, duke of Leucas, had Ladislaus absolve him from his feudal obligations to Achaea (1406) and then, allied with Theodore I Palaiologos, Despot of Morea.

In 1417, the imperial army of Constantinople, led by the despot Theodore II Palaeologus and Emperor John VIII, invaded Achaea.

In 1418, Olivier Franco, a former captain of the Toccos seized Glarentza and imprisoned Benedict Zaccaria, the brother of Centurione, along with his Asenina-Palaiologina princess and children expecting ransom for their release.

[16] In front of the danger of the Palaiologoi, at 1422, the family of Zaccarias, tried to arouse the interest of the Hospitallers of Rhodes for Morea overall and inform them about the intention of Stephen to offer Patras to their order.

The Hospitallers in a letter that they addressed to Centurione, Stephen and also the despot Theodore II refused the offer as they didn't want to be again involved in the domestic business of Morea.

Hopf suggested that Centurione married the niece of Carlo Tocco, a daughter of his brother Leonardo II, whom he names Creusa.

[11] Its evident that the illegitimate son of Carlo, Ercule Tocco, assisted by a small group of Zaccaria soldiers unleashed raids against lands of the despotate of Morea.

[28] From the reign of Centurione survives a document, where we see the prince assigning lands, vineyards, trees and servants to Egidio de Leonessa and his descendants.