Voters in the former Soviet republic of 46 million people are choosing between Prime Minister Yulia Tymoshenko and opposition leader Viktor Yanukovych.
The two candidates have fought a bitter campaign, accusing each other of seeking to rig the vote. Many believe the losing side will contest the results in court and prolong an ongoing political crisis.
RFE/RL correspondent Gregory Feifer, who's in Kyiv, says the race is too close to call, but that most are predicting a victory for Yanukovych, the winner of the election's first round on January 17.
President Viktor Yushchenko was eliminated from the election after a dismal performance in the first round. After casting his ballot today in central Kyiv, he said Ukraine's main task is to show it can conduct a peaceful transfer of power, but that Ukrainians would regret either candidate's victory.
"I think Ukrainians will be ashamed of their choice, but that's also democracy," Yushchenko said.
Tymoshenko has threatened to bring her supporters onto the streets if she deems the vote unfair, warning that the protests would be larger than the 2004 Orange Revolution that brought Yushchenko to power.
Yanukovych supporters have already set up tents along with a stage outside Kyiv's Central Election Commission in preparation for possible postelection protests.
Our correspondent says there are already reports in the local media of electoral violations in several regions.
The election's outcome could be crucial for Ukraine's relationship with Russia as well as the country's ties with the West.
Both candidates say they favor Ukraine's integration in Europe and bolstering ties with Russia. But Orange Revolution heroine Tymoshenko says she wants to bring Ukraine into the European Union in five years.
Casting her ballot in her home town of Dnipropetrovsk today, the 49-year-old fiery former gas tycoon --- once dubbed Ukraine's "gas princess" -- repeated her aspirations for the country's future in Europe.
"I have just voted for a new Ukraine, a Ukraine that is happy and wealthy, beautiful and European," Tymoshenko declared.
Orange Disappointment
Tymoshenko supporters accuse Yanukovych of wanting to return Ukraine to its Soviet past.
After voting in Kyiv, Yanukovych said, "the people of Ukraine deserve a better life, so I voted for positive changes, stability, and a strong Ukraine."
A victory for Yanukovych would represent a remarkable comeback five years after the Orange Revolution swept him out of power. Backed by Moscow in the 2004 presidential election, the then-prime minister was initially declared the winner in results later annulled after hundreds of thousands took to the streets in protest.
But many Ukrainians are now deeply disillusioned with what they say are the Orange leaders' broken promises to clean up rampant corruption and reform the economy. They're also suffering from the effects of a devastating economic crisis.
Whoever wins the presidency will have to reopen talks with the International Monetary Fund, which last year froze a $16.4 billion bailout.
Yanukovych -- a stout 59-year-old with a history of speaking gaffes who enjoys overwhelming support in the country's mostly Russian-speaking east -- has tried to soften his political image since 2004.
In Kyiv, Tatyana Pavlova said she cast her ballot for him. "First of all because he'll be together with Russia," she said. "Our roots are Russian, and we need friendly relations. They also live much better there, they have much higher pensions."
Iryna Moskalyuk said she voted for Tymoshenko only because she's more competent than Yanukovych. "Neither of the current candidates can change anything in the country because they've been in power so many years in different posts and even as president wouldn't be able to do anything differently," she noted.
Ballot stations close at 8 p.m. local time. Preliminary results are expected early on February 8.
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