The top US diplomat will try to explore ways to end the conflict that has claimed more than 5,100 lives in the past nine months, as Washington mulls sending weapons to Kiev.
US Secretary of State John Kerry arrived in Kiev on Thursday in a signal of firm US support for the country amid growing international alarm at a surge in fighting.
He will also unveil $16 million (14 million euros) in fresh US humanitarian aid, particularly to help those displaced in the war-torn east.
Kerry will meet President Petro Poroshenko as well as Prime Minister Arseniy Yatsenyuk and Foreign Minister Pavlo Klimkin, after 19 civilians and troops died in the latest fighting with pro-Russian separatists in the east.
"We have a Russian government that is talking the talk of ceasefire, talking the talk of peace, even as it fuels this conflict," a senior US State Department official said.
European, US and Ukrainian leaders, including Kerry, are to gather in Munich on Friday, along with Russian Foreign Minister Sergei Lavrov.
"So the question is if the governments of Ukraine, of the United States, of Europe are appealing for a new sit-down, will the Kremlin spurn that? Or will they sit down and will they push their proxies to do the same?" the official said.
As the fighting has intensified between pro-Russia separatists and the Ukrainian military, Washington has been reviewing its position to see if it should bow to a growing clamour to send heavy weapons to Kiev.
"We continue to evaluate as the situation on the ground changes the security needs of the Ukrainians... But no decisions have been made," the US official said.