Today's appointment by the supervisory board meeting comes after the previous CEO, Martin Winterkorn, quit the job this week over the scandal, which has damaged the company's reputation and threatens its business.
Volkswagen has admitted to cheating on diesel car emissions test in the US by using a software on 482,000 cars. It has said some 11 million cars worldwide have the software. The company now faces a mountain of difficulties, from class action lawsuits to fixing the software itself.
"We stand by our responsibility," said, adding, however, that "carefulness is even more important than speed."
Mueller said the company would introduce "even tougher compliance rules" and pledged to make VW "an even stronger company."
Winterkorn, who had been CEO since 2007, said he took responsibility for the "irregularities" found by US inspectors in VW's diesel engines, but insisted he had personally done nothing wrong.
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