When Han Solo first arrived on Ventooine, Piin was working with a young man named Phalaf in an attempt to assassinate the wife of the current Satab, Chrysalla. Although Piin deplored violence, he realized that action had to be taken to rid Ventooine of the Satabs. As Chrysalla and her royal entourage drove through the city, Phalaf lobbed an explosive in their midst. Due to Solo's interference, the bomb was destroyed, and the plan was a failure. Piin was only barely able to escape from the Satab's guards, and Phalaf was captured. After seeing Solo's efforts to save a member of the ruling family, Piin labeled the outsider as a threat and decreed that he would have to be killed.
However, in a later incident, Solo risked his life to save several local workers from a Cavern Monster, causing Piin to rethink his decision. The Rov also received word that Solo was to be the next in line to rule Ventooine as a Satab. In an effort to see where Solo's loyalties truly lied, Piin and another priest infiltrated the royal palace where they witnessed the Satab attempting to pass down the source of his power, the shadeshine, to Solo. Unfortunately for the undercover priests, the Satab sensed Piin's presence, and the royal guard quickly took the two priests captive.
A surprise intervention by Chrysalla helped the priests overpower their guards and get away. As soon as the priests were free, they discovered that Solo and Chrysalla had helped kill the Satab, freeing Ventooine from their reign. Piin congratulated the victorious duo, and then oversaw Chrysalla's eventual departure into the Hall of Satabs. After Solo departed Ventooine, Piin helped erect a shrine to Solo at his church. The large statue also contained a memory stone which recounted Solo's experience in overthrowing the Satabs.
During the height of the Galactic Civil War, Piin was still looking after the shrine and fulfilling his local church duties. Inadvertently, the Rebel heroes, Lando Calrissian and Luke Skywalker happened upon the shrine while they were being chased by stormtroopers. Shocked to see such a tribute to their comrade, Skywalker and Calrissian questioned Piin, who played Solo's story through the memory stone. After hearing the tale, Piin helped the Rebels trap the pursuing stormtroopers in the nullification chamber of the Hall of Satabs.