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The shock decision comes after senior members of Germany's Social Democratic Party (SPD) pressured their leader in to waiving the post of foreign minister as part of the grand coalition.
It comes just days after Angela Merkel's conservatives and the SPD agreed to form a coalition government on Wednesday.
But SPD members have the right to veto the deal and reportedly withdrew their confidence in the leader, according to Bild.
In a statement, Mr Schulz said he believed that debate within the SPD risked jeopardising a 'yes' vote among members on whether the party should go ahead with a coalition deal with Mrs Merkel.