The snap election, eight months after a street revolt overthrew Moscow-backed president Viktor Yanukovych, is expected to result in a legislature filled with reformers and nationalists backing President Petro Poroshenko's drive to bring Ukraine closer to the West.
However, Poroshenko's party is unlikely to win a straight majority, meaning he may have to seek a coalition with more radical nationalists suspicious of his attempts to negotiate peace with pro-Russian rebels controlling a swathe of the country's industrial east.
The trauma of some 3,700 deaths in the fighting, and Russia's annexation of the southern Crimean region, set a grim backdrop to an election originally intended as a finishing touch to the pro-democracy revolution.
As a result, the previously peaceful divide between the mostly Russian-speaking and Russia-leaning east and the more Ukrainian-speaking west has become a deadly faultline threatening the entire country's future.
As a result of the turmoil, 27 seats in parliament from the conflict areas will remain empty, election officials say.
Of Ukraine's 36.5 million voters, about 1.8 million live in Russian-controlled Crimea and three million more in separatist-controlled areas of Lugansk and Donetsk provinces - all of them effectively excluded from the election.
Insurgent leaders, who are not allowing polling stations to open in their areas, have announced their own leadership vote, which Kiev does not recognise, on November 2.
A Moscow-backed truce signed by Kiev and the separatists on September 5 has calmed the worst fighting, although there are daily violations around the largest rebel-held city Donetsk.
Ukraine's president visits conflict zone: presidency
Ukrainian President Petro Poroshenko made a surprise election day visit Sunday to the east of the country where troops are fighting against a pro-Russian insurgency.
"I arrived in Donbass," Poroshenko said on his official Twitter account, referring to the conflict region. An accompanying photograph showed him dressed in a camouflage uniform and gazing out of the open door of a helicopter.
There was no information about where exactly the president stopped in the region, only part of which is held by rebels.
The visit came as Ukrainians began voting in a parliamentary election expected to back Poroshenko's pro-Western reforms and test popular support for his plan to negotiate with the insurgents.
The presidency's press office said Poroshenko would return to the capital Kiev to cast his ballot by midday (1000 GMT).
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