Played in the blazing sun, the match lacked some of the tempo of previous games but it did reveal an early candidate for the Golden Ball award, Chelsea striker Arjen Robben.
The fleet footed striker was in everything throughout the 90 minutes and it was only fitting that his name was on the scoresheet after just 18 minutes and later on the man of the match award.
A neat through ball from Arsenal striker Robin Van Persie put the fleet footed Robben into space and despite the heat from the closing defence and bright sun he coolly slotted home to give his side the advantage.
It was the first goal conceded by goal keeper Dragislav Jevric, the only player hailing from Montenegro in the side, in eight matches but it was enough to split the teams.
Serbia and Montenegro coach Ilija Petkovic tried a number of combinations up front during the match, replacing starting strikers Mateja Kezman and captain Savo Milosevic for Danijel Ljuboja and man mountain Nikola Zigic. However they lacked any real cutting edge up front.
A sea of orange: Dutch fans
prepare to celebrate
Dutch striker Ruud van Nistelrooy was similarly disappointing, an audacious flick his only highlight in an anonymous effort which ended on 69 minutes with the introduction of fellow striker Dirk Kuyt.
Earlier, Serbia and Montenegro were happy to sit back and allow their much heralded defence to soak up the Dutch pressure.
They did so comfortably and started to press forward with captain Savo Milosevic their main target.
However once the debutants took their focus off defence Robben made them pay.