A source in Russia's mission to the North Atlantic Treaty Organization said on Wednesday that the Western security alliance had agreed to the appointment.
Rogozin, 44, is due to arrive in Brussels to assume his new post by the end of January. NATO spokesman James Appathurai said in November that the alliance was ready to work with Rogozin.
The politician came to public attention as the leader of the nationalist political bloc Rodina (Motherland) in 2003, when the party won 9.2% of the popular vote.
However, Rodina was banned from the 2005 Moscow Duma elections over a campaign advert deemed racist by a court, which urged voters to "clean Moscow of 'rubbish'."
The foreign affairs committee of Russia's lower house of parliament, previously led by Rogozin, unanimously approved him in November for the post of NATO envoy.
Rogozin has also held the post of the presidential envoy to the Kaliningrad Region, a Russian exclave between Poland and Lithuania.
The politician, characterized by his colleagues as an experienced and flexible diplomat, has said that if appointed NATO envoy he would have to address "very important issues," including international terrorism and the status of Kosovo, adding that "the whole of Serbia is pinning its hopes on Russia."
He has also pledged to focus on the United States' plans to deploy missile defense elements in Europe, a project strongly opposed by Moscow.
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The clash of Russian and Western interests has given rise to a geopolitical battle. German politicians are trying to leave all doors and windows open for dialogue with Russia. Moscow does acknowledge this, and Germany is probably the only country with which it is ready to discuss European security.