Kluivert, 43, has signed a two-year contract at Barca’s La Masia youth system after being fired as Cameroon assistant coach earlier this month.
He scored 145 goals in 308 appearances over six seasons at the Nou Camp, winning one La Liga title.
Kluivert, who won 79 caps for the Netherlands, told Barcelona’s website he was “happy to be back home”.
“I’m looking forward to this new era, with the challenge of keeping Barca among the top teams in the world.”
The Dutchman, who scored 40 goals for his country, started his career at Ajax where he became the youngest scorer in a Champions League final as an 18-year-old.
“I grew up at the Ajax academy, which is very similar to La Masia, and I think I can do a lot for the development of young Barca players,” he said.