The Inter playmaker recently admitted that he would be happy to wear the armband for his country and now the 28-year-old will lead Oranje out on Wednesday
The former Bayern Munich coach was appointed as national team boss in the wake of Bert van Marwijk's disastrous Euro 2012 campaign, which saw them fail to progress beyond the group stage of the competition.
Former skipper Mark van Bommel announced his international retirement at the end of the tournament, and the Inter playmaker admitted that he would be honoured to take over the armband.
Elsewhere, Klaas-Jan Huntelaar, who has often played second fiddle to Robin Van Persie, under Van Marwijk, has been named ahead of the Arsenal man up front.
Meanwhile, Ajax youngster Ricardo van Rhinjn has been handed a start at right-back, with Jetro Willems continuing on the left-hand side of defence, despite criticism of his Euro 2012 performances.
John Heitinga and Joris Mathijsen have kept their slots at the heart of defence and Rafael van der Vaart retains his place as he prepares to make his 100th appearance for his 100th international appearance.
Full line-up: Stekelenburg; Van Rhijn, Heitinga, Mathijsen, Willems; De Jong; Sneijder, Van der Vaart; Narsingh, Huntelaar, Robben
Netherlands and Belgium kick off at 20:45CET on Wednesday.