The invitation to the small Balkan country comes with the West at loggerheads with Moscow over a host of issues, as NATO has responded to the Ukraine crisis with a military upgrade to reassure nervous ex-Soviet states they need not fear a more assertive Russia.
Announcing the move at a meeting of NATO foreign ministers in Brussels, alliance chief Jens Stoltenberg insisted the "historic" invitation to Montenegro was no one else's business and "not directed at anyone."
Stoltenberg said he expected Montenegro's accession talks to be completed early next year but ratification by the 28 NATO member state parliaments could take some time.
Montenegro Foreign Minister Igor Luksic said the decision reflected the great efforts his country had made to modernise and meet western civil society norms.
"It is a great day for my country and for the alliance ... It is great news for the western Balkans, for its unity and security," Luksic said.
"This sort of initiative has the real potential to bring about confrontation. It will not promote peace and stability in the Balkans nor in Europe in general," the Russian foreign ministry said.
"It will only further complicate relations between Russia and NATO."
The tiny Balkans country of just over 600,000 people won its independence in 2006 following the bloody break-up of what was Yugoslavia.
It had been part of a federation with Serbia, a long-time Russian ally which Moscow has always regarded to be part of the same Slav family.
Russia has traditionally been a close ally of Montenegro and several thousand Russians live there, having bought houses and established businesses.
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