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The 33-year-old has decided to call time on his career with the Armenian national team, after a 15-year spell that included 95 caps and 32 goals.
He spent the last six years as national team captain, with his last game coming against Germany in November 2021.
The midfielder posted on social media to announce his decision, saying it was time to concentrate on his club career.
"I think it is the right time," he said. "I have given everything I can possibly give to the national team."
He added: "It was an honour to play for my nation for the last 15 years, and even more so of an honour to captain it for the last six years."
Mkhitaryan has been an almost ever-present for Roma so far this season, earning praise from boss Jose Mourinho for his versatility and the consistency of his performances.
He has scored three goals in 32 appearances so far in all competitions - adding a further seven assists.
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