Ukrainians have been choosing a new president with reports of a high turnout in the west of the country and virtually no voting in the pro-Russian east.
The vote is billed as the most important since the former Soviet republic won independence from Moscow 23 years ago.
The main candidates, including front-runner Petro Poroshenko, known as the "chocolate king" because of his confectionery empire, are promising closer ties with the West in defiance of Russia's President Vladimir Putin.
But the absence of over 15% of the electorate in Crimea, now annexed by Russia, and two eastern regions, where fighting with pro-Moscow rebels continues, may mar any result.
Presidential poll frontrunner Petro Poroshenko speaks after voting in Kiev It could leave the Kremlin questioning the victor's legitimacy, despite Mr Putin's new pledge to respect the will of the people.
Russian Prime Minister Dmitry Medvedev visited Crimea during voting to hand out passports, in a move denounced by Kiev as a "deliberate provocation".
As 12 hours of voting for 21 candidates come to an end at 8pm local time (6pm UK time), exit polls will indicate the result ahead of the official outcome on Monday.
Frontrunner Mr Poroshenko needs to take over 50% of the votes to win outright. If not, a run-off vote will be held on June 15.
Only about 20% of the polling stations in the heavily industrialised, Russian-speaking Donetsk region, which has 3.3 million registered voters, were open, authorities said.
Yulia Tymoshenko votes in Dnipropetrovsk with her husband and daughter None were open in the city of Donetsk, where the streets were empty, and only 426 of 2,430 were open across the region.
Although there was no significant violence, armed pro-Russian militias were seen on the streets in the region with ballot boxes being smashed.
Sky's Katie Stallard, in eastern Ukraine witnessed separatists burning ballot papers in the town of Makiivka.
European election monitors have largely pulled out of the Donetsk region for their own safety, claiming a campaign of "terror" by pro-Russian separatists against Ukrainian electoral officials.
Others also complained of being prevented from voting, in some cases because ballot papers had not been delivered because of security concerns after at least 20 people were killed in the region during fighting over recent days.
UDAR party leader Vitali Klitschko with wife Natalia and brother Vladimir Mr Poroshenko's closest rival is former prime minister Yulia Tymoshenko who remains a divisive figure to many as she is more closely linked with the economic failures that have blighted post-Soviet Ukraine.
"It is time to hold a referendum on joining Nato to restore peace in Ukraine," said Ms Tymoshenko after voting in her native city of Dnipropetrovsk in central Ukraine.
As ousted president Viktor Yanukovich's fiercest rival, Ms Tymoshenko may benefit from the fact that few of the five million voters in his eastern power base regions of Donetsk and Luhansk may be able to cast ballots for any of the candidates.
The voting took place a day after an Italian journalist and his Russian interpreter were killed in eastern Ukraine.
Photojournalist Andrea Rocchelli, 30, and Andrey Mironov, 60, who was also a human rights activist, reportedly died during shelling close to Slavyansk. With them was French photographer William Roguelon, who was injured.
The Italian foreign ministry said the exact circumstances of Mr Rocchelli's death remained unclear because the situation on the ground was "difficult to verify" even for the Ukrainian authorities.
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