Tomorrow's vote comes with tensions running high after a bloody upsurge in fighting in the east, where pro-Russian separatists are fighting against central government rule.
Campaigning is banned on the eve of the vote, but Kiev's interim leaders are planning to attend prayers for peace in the capital's main cathedral.
In what could be a significant move in Ukraine's bitter confrontation with its former masters in Moscow, Russian President Vladimir Putin declared yesterday that he would respect the outcome of the vote.
Putin has in the past given only grudging backing to what Kiev and the West hope will restore stability after months of crisis sparked by the toppling of Ukraine's pro-Kremlin president in February which later saw Russia annex Crimea and pro-Moscow separatists launch an insurgency in the east.
"We understand that the people of Ukraine want their country to emerge from this crisis," Putin said at an economic forum in Saint Petersburg.
"We will treat their choice with respect.
"We are today working with those people who control the government and after the election we will of course work with the newly elected authorities."
But he said Ukraine had descended into "chaos and full-scale civil war", accusing the United States of causing the had caused the crisis by backing the overthrow of Viktor Yanukovych, who fled in February after months of sometimes bloody pro-EU street protests.
The days before the election have been blighted by a resurgence in deadly fighting between the Ukraine military and the rebels who have declared independence in the eastern provinces of Donetsk and Lugansk.
Seven people were killed outside Donetsk city on Friday, a day after the deaths of 19 soldiers in the heaviest loss for the Ukraine military since the conflict erupted in early April.
About 150 people have been killed in the east since then, according to an AFP tally based on UN and Ukrainian government figures.