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Ukrainians are voting for a new president in a repeat ballot called after outrage over fraud led to the cancellation of the result.
Pro-Western opposition leader Viktor Yushchenko is strongly tipped to defeat Prime Minister Viktor Yanukovych, whose 21 November win was widely discredited.
Correspondents say the margin of victory will be almost as important in a country with a sharp east-west split.
About 12,000 foreign observers are monitoring the vote across the country.
In many polling stations, voters here are outnumbered by electoral officials and monitors by two to one, reports the BBC's Yaroslav Lukov.
Ukrainians are not rushing to cast their votes, he says, preferring to take their time as the polling stations remain open until early evening.
But thousands of supporters of Mr Yushchenko, in their distinctive orange colours, are camped out in freezing conditions on the main street in the capital, Kiev.
They have been on the Khreshchatyk since Mr Yushchenko called foul after the November result was announced.
The Ukrainian Institute of Social Research and Social Monitoring Center showed Yushchenko winning with 58.1 percent of the vote and Prime Minister Viktor Yanukovych garnering 38.4 percent. The poll showed 3.5 percent of respondents voting for neither candidate, and the margin of error was 2 percent.
The poll, established and funded by the government, had a sample of 13,500 voters who were questioned in face-to-face interviews at 360 polling stations throughout Ukraine. It was sponsored by nine state academic organizations, including sociologists' associations and six universities.
KIEV, Ukraine - Opposition leader Viktor Yushchenko declared victory Monday in Ukraine's fiercely contested presidential election, telling thousands of supporters they had taken their country to a new political era.
"We have been independent for 14 years but we were not free," Yushchenko told the festive crowd in Kiev's central Independence Square, the center of weeks of protests after the fraudulent and now-annulled Nov. 21 ballot in which Prime Minister Viktor Yanukovych was declared the winner.
Originally posted by Nygdan
t So I am not so sure that things are 'better', in a certain sense, with his win.
Interesting times, right?...
Ukraine's Prime Minister Viktor Yanukovych has refused to concede defeat in the presidential election won by his rival Viktor Yushchenko.
"I will never recognise such a defeat, because the constitution and human rights were violated," he said.
Earlier, international observers praised the conduct of Sunday's re-run vote, held after the second round was annulled over ballot-rigging.
With nearly all votes counted, Mr Yushchenko has an eight-point lead.
The pro-Western opposition leader, who wants Ukraine to push through liberal reforms, is on 52%, against Mr Yanukovych's 44%, official results show.
But Mr Yanukovych said his campaign team had close to 5,000 complaints about how the third round of voting was conducted.