Puyol's playing days came to an end in March 2014 because of a knee injury. In May he joined the clubs management team.
Barcelona sacked their football director Andoni Zubizarreta today and about an hour later Puyol's announcement followed on his Facebook page.
"I have decided to end my working relationship with FC Barcelona," Puyol wrote on his Facebook page.
"I hope to grow both personally and professionally so that, in the future, I can return to this house and give back everything that you have undoubtedly given me during these unforgettable years," he added.
"I remain enormously grateful to the employees, the management, the president and the sports management for trusting me and helping me during this transition which is not easy."
Puyol was one of the most successful centre-backs in world football over the past decade as he won three Champions Leagues and six La Liga titles with his boyhood club.
He also scored the winner for Spain in their 1-0 win over The Netherlands in the 2010 World Cup finals in South Africa.