The 29-year-old Arsenal player becomes the third squad member to retire since the end of the World Cup following captain Philipp Lahm and record goalscorer Miroslav Klose.
"I am proud to have had 10 years in the team, five big tournaments, 104 caps and to have won the World Cup," Mertesacker said in a statement on Friday.
"That is a magnificent end and for me it is the right time to leave the national team and make way for the new generation."
Mertesacker, who came on in the last minute of extra-time in Germany's 1-0 final win over Argentina, also told the Sueddeutsche newspaper he wanted to determine when his international career finished.
"First and foremost it was about me... being able to say when the chapter ended," he said.
Tall and powerful, the defender was Germany's first choice centre back for a decade after winning his first cap in 2004.
Mertesacker lost his place when coach Joachim Loew opted for Jerome Boateng and Mats Hummels in the middle of the back four when they crushed hosts Brazil 7-1 in the semi-finals of the World Cup.
Loew started with the same pair in the final as well.
"That tournament was a golden finale," Mertesacker said. "Now I want to be Premier League champions with Arsenal and also attack the Champions League."
Mertesacker played in three World Cups and also featured at the 2008 and 2012 European Championships.
"Per personifies dependability and I could always rely on him," said Loew. "In Brazil he was one of our most important players who inspired the team and set the direction."
Arsenal launch their Premier League season with a London derby against Crystal Palace on Saturday.
(Editing by Tony Jimenez)
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