Holland were stunned by Belgium, Argentina beat Germany and Russia drew in Fabio Capello's first match as manager on a busy night of international friendly action.
Holland endured a miserable Euro 2012 and it was another painful evening in Brussels as Belgium ran out 4-2 winners to ruin Louis van Gaal's first game in charge
Luciano Narsingh and Klaas-Jan Huntelaar temporarily put Oranje ahead after Christian Benteke had opened the scoring for the home side, but goals from Dries Mertens, Romelu Lukaku and Jan Vertonghen turned the match in Belgium's favour.
Argentina got the better of 10-man Germany at the Waldstadion in Frankfurt, with goalkeeper Ron Robert Zieler sent off on the half-hour mark in a 3-1 win for the visitors.
Lionel Messi missed the resulting penalty after Zieler's dismissal but later did manage to score after an own goal from Sami Khedira had broken the deadlock, with Angel di Maria adding a third before Benedikt Howedes grabbed a late consolation for the hosts.
Euro 2012 champions Spain warmed up for the start of the World Cup qualification campaign with a 2-1 victory over Puerto Rico.
New Arsenal signing Santi Cazorla fired Spain ahead in the 42nd minute and former Gunners captain Cesc Fabregas then added a second on the stroke of half-time, before Marc Cintron pulled one back for Puerto Rico.
Capello's reign as Russia manager started with a 1-1 draw against Ivory Coast, as Alan Dzagoev's opener was cancelled out by an equaliser from Max Gradel.
Nelson Oliveira and Cristiano Ronaldo netted for Portugal in a comfortable 2-0 success at home to Panama.
Brazil cruised to a 3-0 victory over Sweden thanks to a double from Alexandre Pato and a goal from Leandro Damiao.
France and Uruguay played out a goalless draw, while the game between Ukraine and Czech Republic also ended 0-0.
Eduardo scored twice for Croatia but Igor Stimac's side were beaten 4-2 by Switzerland courtesy of goals from Granit Xhaka, Tranquillo Barnetta and a Mario Gavranovic brace.
Fulham duo Brede Hangeland and John Arne Riise were on the losing side despite both scoring for Norway, with goals from Vasilis Torosidis, Kyriakos Papadopoulos and Konstantinos Mitroglou sealing a 3-2 win for Greece.
Slovakia came from behind to beat Denmark 3-1, while elsewhere Slovenia edged out Romania in a 4-3 thriller, Austria beat Turkey 2-0 and Euro 2012 co-hosts Poland lost 1-0 to Estonia.