The decision, described by NATO head Jens Stoltenberg as “historic”, comes 16 years after the alliance bombed Montenegro during the Kosovo war, when it was still part of Yugoslavia.
Russia has reacted to the news. Montenegro’s accession would result in “retaliatory actions”, said a spokesman for Russian President Vladimir Putin.
Accession talks are expected to take about a year to complete.
The invitation to Montenegro is NATO’s first expansion into Eastern Europe since Albania and Croatia joined in 2009.
The mountainous Adriatic state of 650,000 people has a small military with about 2,000 active members.
NATO diplomats say it sends a message to Russia that it cannot veto the alliance’s expansion – but Russia has said it will retaliate.
“The continued eastward expansion of NATO and NATO’s military infrastructure cannot but result in retaliatory actions from the east, i.e. from the Russian side, in terms of ensuring security and supporting the parity of interests,” Vladimir Putin’s spokesman Dmitry Peskov said.
Dmitry Peskov added that it was too early to specify what the retaliatory actions would be.
Montenegrins themselves remain divided over joining.
Many remain angry that NATO bombed Serbia and Montenegro in 1999 as part of a strategy to halt the killing and expulsion of ethnic Albanians in Serbia’s then southern province of Kosovo.
Montenegro has also seen an influx of Russian money, homebuyers and tourists since splitting from Serbia in 2006.
Milo Djukanovic’s government – which is in favor of joining – has resisted calls from some opposition parties for a referendum on the issue.
However, NATO diplomats point to polls that suggest public opinion is narrowly in favor of joining.
Besides Montenegro and Georgia, the other current candidates for NATO membership are Bosnia and Herzegovina and Macedonia.
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