Mr Rogozin is opposed to Kosovo breaking away from Serbia
Dmitry Rogozin will become Moscow's permanent representative to the military alliance.
A foreign policy hawk, Mr Rogozin is a former head of the anti-immigration Russian Motherland party.
He has previously warned Moscow the Western military alliance poses a threat and called for Russia to stand firm against independence for Kosovo.
Mr Rogozin has also served as Russia's representative to the Parliamentary Assembly of the Council of Europe (Pace), a multi-national Strasbourg-based human rights body.
In 2005, Russia's Supreme Court banned Motherland from taking part in elections to the Moscow City Council. The court ruled that a campaign advertisement in which Mr Rogozin appeared was racist.
Mr Rogozin's appointment is a reflection of Russia's more assertive stance towards the West, the BBC's James Rodgers reports from Moscow.
Nato is viewed with great suspicion in Russia - politicians and ordinary people alike see the alliance's post-Cold War eastward expansion as blatantly hostile, our correspondent says.Mr Rogozin has previously called for Russia to rearm to counter the perceived threat.