Last winter's revolution in Kiev upset Russian President Vladimir Putin's plans to enlist Ukraine in a new, Kremlin-led bloc that could rival both Nato and the European Union.

And Moscow had set Kiev's exclusion from all military blocs as a condition for any deal on ending the pro-Russian uprising that has killed 4,700 in the eastern Ukrainian rust belt in the past eight months.

Putin's view of Nato as modern Russia's biggest threat has only been reinforced by this year's dramatic spike in East-West tensions over Ukraine.

"In essence, an application for Nato membership will turn Ukraine into a potential military opponent for Russia," Russian Prime Minister Dmitry Medvedev warned in a Facebook post on Monday.

He said that Ukraine's rejection of neutrality and a new Russian sanctions law that US President Barack Obama signed on Friday "will both have very negative consequences".

"And our country will have to respond to them," Medvedev added.

Perhaps the most immediate threat will be to delicate peace talks this week in the Belarussian capital Minsk that Poroshenko announced on Monday.

Poroshenko said the deal for Kiev and rebel negotiators to meet in the presence of Russian and European envoys on Wednesday and Friday was struck during a joint call with German Chancellor Angela Merkel and French President Francois Hollande the West's top mediators on Ukraine.

The last two rounds of Minsk consultations in September produced a truce and the outlines of a broader peace agreement that gave the two separatist regions partial self-rule for three years within a united Ukraine.

A pro-Russian separatist stands guard near Donetsk's Sergey Prokofiev International Airport (Reuters)

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Ukraine takes historic step toward Nato membership