In 1985, Puccio and Giuseppe Lucchese murdered their boss, Pino Greco, on the orders of Salvatore Riina. As a reward, Puccio was granted the prestigious position of chief of the Mafia family and the mandamento of Ciaculli.
Late in 1986, Puccio was captured and held on suspicion of multiple murder. On May 11, 1989, he was beaten to death in his cell at the Ucciardone Prison in Palermo by fellow inmates Antonino and Giuseppe Marchese, two other Mafiosi who had been acting on Riina's orders. In 1990 an informant, Francesco Marino Mannoia, subsequently claimed that Puccio had become the boss of the Ciaculli Family after the murder of his predecessor, Giuseppe Greco, in 1987. Puccio had been planning on taking on the Corleonesi and overthrowing Riina and Bernardo Provenzano as the most powerful mafiosi in the Sicilian Mafia. Riina had found out about this conspiracy after Corleonesi mafioso Leoluca Bagarella had been let in on the plan but, for whatever reason, had treacherously revealed all to his boss.
Antonino and Giuseppe Marchese - both nephews of another Mafia boss, Filippo Marchese - claimed they had killed Vincenzo Puccio in self defence after a fight, but their claim was ruined by Riina who deliberately had Vincenzo Puccio's brother, Pietro, killed that same day outside of prison. This meant the Marchese brothers had no chance of convincing a jury they had acted in self defence during a spontaneous fight when their victim's brother had been very deliberately shot dead that same day. They were both sentenced to life imprisonment for Puccio's murder.
Puccio's successor as head of the Ciaculli Mafia Family was Giuseppe Lucchese.
Giuseppe Marchese subsequently cooperated with the government and became a pentito. He confirmed the details Francesco Marino Mannoia had given previously of the events leading to Puccio's killing on Riina's orders.