GENEVA--Foreign ministers from Russia, Ukraine, the U.S. and European Union were starting talks in Geneva Thursday morning in the biggest diplomatic effort so far to ease tensions between Kiev and Moscow.

The meeting will be the highest-level direct talks between Russia and Ukraine since Moscow annexed the Crimea region and placed tens of thousands troops on the border. It comes as three pro-Russian protesters were killed in an overnight clash with Ukrainian authorities at a military installation in the southeast of the country.

Russian Foreign Minister Sergei Lavrov was the last of the four ministers to reach in the Swiss lakeside city, arriving Thursday morning. U.S. Secretary of State John Kerry met with EU foreign policy chief Catherine Ashton before Mr. Lavrov arrived.

Western officials said ahead of the meeting they were expecting no sudden breakthrough in calming the crisis.

The talks will seek to contain the escalating crisis and start a process where tensions can be eased in coming weeks ahead of presidential elections in Ukraine, due May 25, the officials said.

The discussions will focus on the growing crisis in eastern Ukraine, where pro-Russian separatists have occupied government buildings in a number of towns. Ukraine has sent troops to oust the separatists that Kiev and Washington say are backed by Moscow.

"This will be the first opportunity for this contact group to meet," said White House spokesman Jay Carney late Wednesday. "And we expect the conversation to focus on the need to de-escalate, the need for Russia to demobilize its troop presence on the border with Ukraine, the need for armed separatist groups within Ukraine to disband and disarm."

The U.S. and the EU have sought to raise the ante on Russia to engage in meaningful talks on Thursday.

Mr. Carney said Wednesday the U.S. had "additional sanctions prepared and we'll impose them as appropriate."

The EU is currently deciding how many Russian officials to add to a travel ban and asset freeze list and the bloc's executive, the European Commission, on Wednesday sent details to member states about possible broader sanctions measures.

Russia has denied it is directly involved in the latest events in eastern Ukraine. It has demanded Kiev move to shore up the rights of Russian-speaking Ukrainians and has urged greater autonomy for Russian dominated provinces.

The North Atlantic Treaty Organization also said Wednesday it would increase its flights over the Baltic nations and send ships to the Mediterranean and Baltic seas in response to Russia's threat to Ukraine.

Naftali Bendavid, Jay Solomon and Lukas I. Alpert contributed to this article.

Write to Laurence Norman at laurence.norman@wsj.com

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