The 36-year-old former defender spent 15 trophy-laden years at the club, winning La Liga on six occasions and three UEFA Champions League titles.
However, in March he announced he was to end his playing career with the Catalan giants after an injury-plagued 2013-14 campaign.
It was revealed on Friday that he would become part of the sports management team at Barca currently headed by Andoni Zubizaretta, with the news confirming Puyol's retirement as a player.
"I want to thank Barcelona for all that it has given me before and for this chance that has arisen now," he told the club's official website.
"I will try to the very best I can, and especially to learn a lot.
"I have always played football and tried to do so as well as possible, and I'll be doing the same with this.
"Now I need some time to rest and continue treatment on my knee, but I am really looking forward to it. I am very excited about this new stage of my life."
Zubizaretta believes the appointment of Puyol represents a great opportunity for the club to tap into his wealth of knowledge.
"Puyol is joining the football department and we will be seeking to exploit and learn from all of his experience," he said,
"We also want people to realise how much he knows. He will be an assistant to the sports management, so he'll be working with me on club projects, both internally and externally.
"We'll be working in more external areas like marketing and finance, and in the technical secretary area. I am sure I'll learn a lot from him."
