Ukrainian President Petro Poroshenko is due to take part in talks with his Russian counterpart, Vladimir Putin, at a summit in Minsk, capital of Belarus.
Fighting in eastern Ukraine has left more than 2,000 people dead since April
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The meeting comes amid rising tension between the two countries over Ukraine's military campaign against pro-Russian separatists.
Ukraine said on Monday that its troops had captured 10 Russian servicemen in eastern Ukraine.
Russia has repeatedly denied supporting the rebels.
More than 2,000 people have died in months of fighting between Ukrainian forces and separatists in Donetsk and Luhansk regions.
The two regions declared independence from Kiev following Russia's annexation of the southern Crimean peninsula from Ukraine in March.
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The BBC's David Stern in Kiev says Tuesday's talks are under the auspices of the Moscow-led Eurasian Customs Union, which also includes Belarus and Kazakhstan, and that it is still unclear whether Mr Putin and Mr Poroshenko will meet separately.
Source: BBC