Spain lost at the scene of their 2010 FIFA World Cup final triumph on Tuesday after a shock 1-0 defeat to South Africa.
Vicente del Bosque s men returned to Soccer City in Johannesburg for the first time since Spain beat Netherlands 1-0 in the final of the World Cup three years ago.
However, it proved a bittersweet occasion as striker Bernard Parker scored the only goal of the game in the friendly with a delicate finish after being played through by Thabo Matlaba.
There was late controversy, though, as Spain made a seventh substitution the most permitted in a friendly is six as goalkeeper Pepe Reina replaced the injured Victor Valdes nine minutes from time.
Germany claimed victory as rivalries with England were renewed, Per Mertesacker s second-half header inspiring the visitors to a 1-0 success as Joachim Low s men condemned the hosts to consecutive defeats at Wembley for the first time since 1977.
Netherlands extended their unbeaten run to 17 games with a 0-0 draw against Colombia, despite Jeremain Lens dismissal in a bad-tempered affair at the Amsterdam Arena.
Belgium have been touted as outsiders for next year s FIFA World Cup, but they are still yet to beat Japan in their history after falling to a 3-2 home loss to Alberto Zaccheroni s men.
The hosts did take the lead through Kevin Mirallas before Yoichiro Kakitani s header and a strike from Keisuke Honda turned the game on its head.
Mainz attacker Shinji Okazaki added to Japan s lead and the visitors held on for a deserved win, despite Toby Alderweireld s late header.
Gibraltar marked their historic debut appearance on the international scene with a credible 0-0 draw with Slovakia.
Fyodor Smolov and Dmitriy Tarasov were on target as Russia came from behind to beat South Korea 2-1, while Marc Janko scored the only goal in Austria s 1-0 victory over United States.
Burak Yilmaz scored in the 89th minute to give Turkey a 2-1 win over Belarus and Republic of Ireland manager Martin O Neill remains undefeated following his side s goalless stalemate with Poland.
Valter Birsa s second-half strike gave Slovenia a 1-0 win over Canada, while Scotland beat Norway by the same scoreline thanks to a deflected effort from Celtic midfielder Scott Brown.
Elsewhere, Malta overcame Faroe Islands 3-2, Liechtenstein lost 3-0 to Estonia and Kyrgyzstan drew 0-0 with Azerbaijan.
