The heavyweight clashes were the stand-out matches on a night of almost 40 friendlies around the world, where swathes of debutants stepped into the international limelight as their coaches took the opportunity to experiment.
There were a clutch of impressive away wins in Europe as France beat England 2-1 at Wembley, Belgium upset Russia 2-0, Norway overcame Ireland 2-1 and Greece defeated Austria 2-1.
World Cup runners-up Netherlands beat Turkey 1-0 but several of Europe’s other big guns failed to ignite.
Germany were held to a goalless draw in Sweden, Italy, with four debutants, drew 1-1 with Romania in Austria in a game marred by racist chanting from Italian fans, while Denmark against Czech Republic also ended 0-0.
In the night’s two Euro 2012 qualifiers, Croatia beat Malta 3-0 and Finland thrashed San Marino 8-0.
The World Cup is becoming a distant memory for Spain, who since their July triumph have lost 4-1 to Argentina and made hard work of beating Scotland in a Euro 2012 qualifier.
Spain beat Portugal 1-0 in the second round in South Africa but, despite having a near-full strength side, they were outclassed and slipped to their worst defeat since Scotland beat them 6-2 in 1963.
Carlos Martins just before the break and Helder Postiga with a backheeled goal just after, put the hosts in control.
A second for Postiga and Hugo Almeida’s stoppage-time fourth had the home fans in dreamland and brought a sudden halt to the pre-match bid-boosting back-slapping.
The money-spinning duel in the desert between Brazil and Argentina promised much but delivered only once a cagey 90 minutes had been played.
Twice former world player of the year Ronaldinho, left out of Brazil’s World Cup squad, looked lively on his comeback and almost scored with a backheel but in the second minute of stoppage time Messi showed why he inherited the crown.
The striker picked his way through a ragged Brazilian defence showing great control before angling in a low shot.
It was Argentina’s first win over Brazil is six matches since 2005 and gave Sergio Batista a winning start as full-time coach following his three interim games in charge.
INEXPERIENCED ENGLAND
France continued their rehabilitation under Laurent Blanc by outplaying an inexperienced England team and handing them their first home defeat under Fabio Capello.
Karim Benzema and Mathieu Valbuena finished off good passing moves to put the visitors 2-0 up before substitute Peter Crouch maintained his remarkable scoring record with his 22nd goal in 42 internationals seconds after coming on at the death.
Klaas-Jan Huntelaar is another on a hot streak as he headed his ninth in five internationals to secure Netherlands’ win.
The Dutch had only five survivors from their World Cup final team while Turkey coach Guus Hiddink gave five players their debuts.
Seventeen-year-old Belgium striker Romelu Lukaku added to his burgeoning reputation by scoring both goals, his first in internationals, in the win over Russia in Voronezh.
Another 17-year-old had a night to remember in Cape Town as debutant Juan Agudelo scored five minutes from time to give a makeshift United States team a 1-0 win over South Africa.
Croatia marked the 20th anniversary of their first match as an independent nation by beating Malta 3-0 with two long-range goals for Niko Kranjcar and one for Nikola Kalinic to go top of Group F, two points ahead of Greece and four ahead of Georgia.
Mikael Forssell hit a second-half hat-trick as Finland hammered San Marino 8-0 in Group E but, having lost their first three matches, they remain the longest of qualifying shots.
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