Candidates came to a last-minute agreement earlier this week to agree and sign the voter lists required for the election to take place.
In 2012, ex-President Mohamed Nasheed was forced from office, sparking a political crisis.
Mohamed Nasheed is seeking to regain power at these elections.
Tensions are high after one vote was annulled and a re-run halted by police.
“Voting got underway at 475 polling booths across the Maldives and several foreign capitals where Maldivians live,” Elections Commission official Aishath Reema told the Agence France-Presse news agency.
Supporters of Mohamed Nasheed’s opposition Maldivian Democratic Party allege the government and judiciary are attempting to influence the electoral process, fearing he will return to power.
Mohamed Nasheed, won the country’s first-ever democratic vote in 2008, ousting Maumoon Abdul Gayoom, who ran the country autocratically for three decades.
His main rival at the ballot box is Maumoon Abdul Gayoom’s half-brother, Abdullah Yameen. The other major contender is Gasim Ibrahim, a wealthy resort owner and a former minister under Gayoom.
If no candidate gets more than 50% of the vote then a second vote is scheduled to take place on Sunday.
In a vote on 7 September, Mohamed Nasheed led with 45% of the vote, while Abdullah Yameen and Gasim Ibrahim trailed with 25% and 24% respectively.
President Mohamed Waheed Hassan Manik got 5% and later bowed out.
That vote was annulled by the Supreme Court after Gasim Ibrahim alleged irregularities, despite observer groups deeming the vote free and fair. The court also introduced new guidelines for elections.
Police halted the planned re-run on 19 October saying the guidelines had not been met, after both Ibrahim Gasim and Abdullah Yameen failed to approve the registry of voters.
According to the Maldives constitution, a new president has to be in place by November 11 when the current presidential term ends.
Mohamed Nasheed was forced from office in February 2012 in what he has described as a coup. Mohamed Waheed, who succeeded him, claims Mohamed Nasheed resigned of his own accord in the face of opposition demonstrations.
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