The nomination has yet to be signed by the president.
Rogozin, 44, is a member of A Just Russia faction and former leader of the Rodina party, which was banned at the 2005 Moscow Duma elections over a nationalist campaign video calling to "free Moscow from the rubbish."
The lawmaker, also a former chairman of the State Duma committee for foreign affairs, was earlier considered a pro-Kremlin politician and held the post of presidential envoy to the Kaliningrad Region, a Russian enclave between Poland and Lithuania.
"[The Federation Council's foreign affairs committee] came to the conclusion that he [Rogozin] could find new ways to strengthen complicated, but extremely important NATO-Russia relations," Vasily Likhachev, a deputy chairman of the Federation Council's foreign affairs committee, said.
Rogozin, characterized by his colleagues as an experienced and flexible diplomat, said if appointed to the post he would have to solve "very important issues," including international terrorism and the status of Kosovo, adding that "the whole of Serbia is pinning its hopes on Russia."