Preliminary results indicate former Prime Minister Milo Djukanovic has won more than 50 per cent of the vote, thus avoiding a run-off.
The pro-Western economist led Montenegro to independence from Serbia in 2016 and into North Atlantic Treaty Organisation previous year - now he wants to take the predominantly Orthodox country, a part of which has strong pro-Russia sympathies, into the European Union.
With almost all the votes counted, Djukanovic won about 53 percent while his main opponent, Mladen Bojanic, won 33 percent, according to preliminary results.
If confirmed in the official vote count, the result will present a major boost for Djukanovic and his ruling Democratic Party of Socialists. Party leader Milos Nikolic said at the party's headquarters: "Djukanovic is the new president of Montenegro. there will be no second round". President Filip Vujanovic, also of the ruling party, was not running due to term limits.
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Having dominated politics as either prime minister or president of the former Yugoslav republic of about 620,000 people, Djukanovic stepped down as prime minister in 2016. "I will continue the struggle to liberate Montenegro from Djukanovic's dictatorship".
Approximately 530,000 voters can choose among candidates.
The opposition says Djukanovic has ties to the mafia, an accusation he has denied.
The country has also been marred by organized crime, with about 20 people killed by assassinations or vehicle bombs over the last two years.
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Bojanic conceded defeat, saying: "Montenegro chose the way it chose".
"I understand this election result as a confirmation of Montenegro's evolution to achieve European values, European standards and full membership in the European Union", Djukanovic said before opening a bottle of champagne.
Earlier in the campaign he accused Djukanovic of being "the creator of the instability and chaos that we witness in the streets of Montenegro". The average salary in Montenegro sits at around €500 ($615) and unemployment is more than 20 percent.
The EU in its 2016 country progress report told Montenegro it should continue its efforts to reduce organised crime, in particular on human trafficking and money laundering, and also noted the problem of worldwide cigarette smuggling through the port of Bar.
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Montenegro's presidency is a ceremonial post, but is expected to become the real seat of power in the country if 56-year-old Djukanovic is confirmed as the victor.