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Two candidates who came third and fourth, former central bank chief Sergey Tigipko and former parliament speaker Arseniy Yatsenyuk, said they would not come out in support of any candidate in the second round.
An aide to Tymoshenko, a populist who amassed a fortune in her years in the gas industry, said however that her camp hoped to meet Tigipko in the next few days.
Widespread disenchantment with politics and anger over a deep economic crisis marked the vote.
Voters appear to have punished incumbent President Viktor Yushchenko, one of the architects of the Orange Revolution, for the country's recent political in-fighting.
The Western-funded National Exit Poll Consortium gave Yushchenko just 6 percent.
Both the leading candidates have pledged to seek better relations with neigbouring energy supplier Russia, in part to avoid the spats of recent years which led to supply cut-offs affecting parts of Europe.
Yanukovich has called for a strong, independent Ukraine following a neutral path and not joining NATO or any other bloc. He attacked Yushchenko for excessively confrontational policies towards Russia and says Ukraine's real enemy is poverty.
His Party of the Regions is allied to the Kremlin's United Russia party but Yanukovich has been careful to avoid appearing as Moscow's stooge this time around.
He was tarnished by a scandal in 2004, when he initially claimed victory in an election tainted by allegations of fraud and was subsequently swept aside by the Orange Revolution.
Although Tymoshenko initially had stormy relations with Russia, she has tried to patch up her links to the Kremlin of late. Russia's Prime Minister Vladimir Putin has described her as a person Moscow can do business with.
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