The retired striker is flattered to have been given the chance to work with the Oranje's senior team after previously representing the side during his playing daysNetherlands coach Louis van Gaal.
Together with Danny Blind, the former striker will work alongside the 60-year-old, who was, earlier in the month, unveiled as the new Oranje coach following the post-Euro 2012 dismissal of Bert van Marwijk.
Kluivert, who will continue to coach Twente's youth team, spoke of his excitement to have formed part of his country's coaching set-up, having represented the national side 79 times between 1994 and 2004.
"I am very honoured to take this job," he told reporters. "It is great that I will have the chance to work with the best Dutch players.
"I played for the Oranje for quite some years, so it is great to return.
"I would also like to thank Twente because they are letting me combine my job in the youth team with my role in the national side."
Kluivert retired from football in 2008 after an illustrious career which reached its peak during his six-year spell at Barcelona, where he scored 90 Liga goals.
Netherlands will take on Turkey, Hungary, Romania, Estonia and Andorra in their World Cup 2014 qualifying group.