Archaeological evidence suggests the area has been inhabited since prehistoric times, as indicated by the presence dolmens and menhir structures.

The exact origin of its foundation is uncertain: one theory suggests Zollino was established as a Iapygian colony from the nearby village of Apigliano.

Another theory proposes that Zollino began as a rural settlement of people from the nearby town of Soleto, from which its ancient name Solino is believed to have originated.

In 1384, Mary of Enghien included Zollino as part of her dowry upon her marriage to Raimondo Orsini del Balzo, Count of Soleto.

After his death, the Chiaromonte family, led by Tristan of Clermont, retained feudal rights over Zollino through his marriage to Catherine of Taranto, the daughter of Raimondello.