The four-time champions lost to South Korea 2-0 on Wednesday - conceding two stoppage time goals - while knowing a 1-0 victory would have been enough for them to advance.
The four-time winners, who had not been eliminated in a World Cup first round since 1938, were a shadow of their once dominant selves, managing only two goals in their three group games.
South Korea coach Shin Tae-yong says his team have just a "one percent chance" of beating Germany and even star forward Son Heung-min played down their chances of an upset.
After defeats to Sweden and Mexico, South Korea were expected to bow out of the tournament against a Germany side who needed a win, but a major surprise occurred in Kazan.
Mexico fans went insane following South Korea's late goals against Germany, having feared they could be set to crash out of the tournament despite a scintillating start to the campaign.
Grateful Mexicans gathered at the embassy after South Korea's win secured Mexico's place in the round of 16 in Russian Federation.
Goretza nearly put Germany in front two minutes after the restart but was thwarted by a superb stop from Jo Hyeon-Woo - and then news filtered through of Ludwig Augustinsson's opener for Sweden.
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Jo's biggest save came in the 47th minute, just as the match started opening up following a lackluster, scoreless first half.
Korea finished third in Group F, and Germany left the World Cup in last place in the group. It looked as if South Korea would be heading home with zero points and three defeats from three games.
Mexico take on the mighty Brazilians in Samara on Monday, hoping to progress to the quarter-finals for the first time since 1986.
But it was a bittersweet victory for the South Koreans, who still failed to advance to the round of 16 despite their performance against Germany.
Germany was becoming desperate but Cho was vast in the goal yet all expected the world champ to do what it always does: get a goal when needed.
Supporters of the German national football team react as they attend a public viewing event at the Fanmeile in Berlin to watch the Russian Federation 2018 World Cup Group F football match between South Korea and Germany on June 27, 2018. South Korea have smaller players, very fast players.
The teams continued to trade chances, with Son rolling one just left of the goal in the 78th minute, and Hummels missing the target with a header in the 86th. And though a draw would still have knocked Germany out of the World Cup, South Korea made sure they paid dearly for some sloppy play.
Throughout the match, Korea managed to create chances, but struggled to convert them into a shots on goal.