Supporters who made the trip to Russia were reduced to tears after the embarrassing 2-0 loss in Kazan.
German fans were on the edge of their seats for much of the must-win game but their hopes were severely dented after a 92nd-minute goal from South Korea.
There was still a slim chance of salvaging three points in the remaining six minutes of stoppage time, but Germany were left stunned after goalkeeper Manuel Neuer pushed up to the half way line leaving an open net for Tottenham forward Son Heung-Min to walk in a second.
Despite storming to victory in the 2014 World Cup in Brazil, Germany fell at the first hurdle in Russia, finishing behind South Korea, Mexico and Sweden to come last in their group.
The result means England, if they are able to progress to the quarter finals, will not have to face the reigning champions.
Germany were hotly-tipped to reach the finals in this year’s tournament, with Joachim Low’s side topping FIFA’s world rankings.
They went into today’s game needing nothing less than three points, which would have seen them finish second above Mexico on goal difference.
But despite dominating possession, the Germans managed just six shots on target.
Today’s defeat marks the first time since 1938 that a German or West German side has failed to progress past the group stages.
In Group F’s other fixture, Sweden hammered Mexico 3-0 to finish top of the group.
Mexico finished second on goal difference.
South Korea, despite their dramatic win against Germany, have been knocked out after finishing third.
England continue their World Cup campaign tomorrow with a difficult fixture against Belgium, but both teams have already secured their place in the last 16 after winning their first two games.
The World Cup ‘champions curse’ has seen three out of the past four winners crash out in the group stages.
France lifted the trophy in 1998, but were knocked out early in 2002 despite an all-star squad.
In 2010, Italy began the tournament as defending champions but also failed to progress past the group stage.
Most recently in 2014’s World Cup, Spain went out in the groups after being hammered 5-1 by the Netherlands before losing 2-0 to Chile.