The union of Serbia-Montenegro, the last vestige of the former Yugoslavia, was created in 2003, but the two regions have been together in some form of joint state for almost a century.
It was created with the mediation of the European Union, which feared further fragmentation in the Balkans.
Montenegro's government says independence will open the way to economic prosperity in the European Union.
The EU this month froze talks on closer ties with Serbia-Montenegro due to Belgrade's failure to arrest fugitive war crimes suspect Ratko Mladic, and the independence camp has used this argument in favour of separation.
The two republics already have different laws, economic policy and currencies, sharing only five ministries that supervise defence, diplomacy and minority rights. Their joint parliament barely meets.
Those in favour of keeping the union with Serbia say it is a risky venture for the country of 650,000 to go it alone.
Pro-unionists uphold the long historical and cultural link with Serbia and say Montenegro needs the jobs, education and health care their larger neighbour can provide.
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