Elections three weeks ago produced no clear winner after Maumoon Abdul Gayoom, who has run the Indian Ocean archipelago unchallenged for 30 years, failed to deliver a knock-out blow to second-placed Mohamed "Anni" Nasheed.
Tuesday's vote will see the Maldives' first elected president following political reforms to the Muslim nation, known for its luxury holiday resorts, introduced in the wake of pro-democracy protests and international pressure.
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The two rivals held final campaign rallies on Sunday night in the capital Male where more than a quarter of the 208,000 electorate is concentrated.
Gayoom, who has ruled since 1978, was expected to receive additional votes this time around from supporters of a moderate opposition candidate who finished behind Nasheed in the first vote, the leader's spokesman said.
"What we really need is another 10,000 votes and Gayoom is comfortably home. But for the opposition, they need to get much, much more than that," spokesman Mohammed Shareef said.