Stoppage-time goals to Kim Young-gwon and Son Heung-min condemned Joachim Loew's side to finish bottom of their group.
South Korea added one more as time expired, Son tapping in after Manuel Neuer had gone up the pitch as Germany searched for a goal.
In the other Group F match, in Ekaterinburg, Sweden clinched a 3-0 victory over Mexico, meaning a win against South Korea would have been enough for Germany to progress.
This was South Korea's first win at the 2018 World Cup after losing 1-0 to Sweden and falling 2-1 to Mexico.
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Jacob Rabon IV tweeted two of the photos with the caption: 'I can't believe childhood is cancelled'. Many kids grew up watching Geoffrey the Giraffe in TV commercials.
The South Koreans played aggressively in the first half and waited patiently for opportunities toward the end when the four-time champions pressed hard to score and get a victory that would have sent them through ahead of Mexico on goal difference.
Since group stages were introduced in the World Cup in 1950 - though they missed out on participation in that edition - Germany have failed to advance to the next stage of the tournament for the first time. "I think we kept trying to turn it all around". South Korea had pulled off a miracle.
"We beat the world champions from the last World Cup and now I'm looking forward to the next World Cup".
In a wide open Group F, all they could hope was an upset result in the other match featuring defending champion Germany against South Korea.
"I have to say that we qualified because we beat Germany and Korea, but nevertheless I am very hurt", coach Juan Carlos Osorio said.
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Seems like a natural step after Jonas vacationed with the former Miss World's family and friends in Goa just earlier this week. Jonas did it by posting a picture of Priyanka Chopra on his Instagram Stories with the caption "Her" and the heart emoji.
Mexico was the only team to have won both of its opening games yet still be faced with a realistic chance of being knocked out, and the pressure showed.
Germany's team of superstars could only look on in shock in the final minutes of the match as U.S. referee Mark Geiger called for the video assistant referee to intervene after the unmarked Kim had bundled his shot past Germany 'keeper Manuel Neuer from a corner early in stoppage time.
He said: "Until quite recently, we have probably been the most consistent, in terms of performance, team in the past 10, 12 years".
South Korea's goalkeeper Cho Hyeon-woo made a fine one-handed save from Leon Goretzka's header and Timo Werner volleyed wide from near the penalty shot.
German defender Mats Hummels said the early exit was "really bitter" for his side.
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Defending champion Garbiñe Muguruza is seeded third, with last year's runner-up Venus Williams seeded ninth. Wimbledon will release the draw on Friday. "I have tried and I should be seeded".
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