Biden's two-day visit comes with the clock ticking on a White House warning of further sanctions against Moscow if it fails to implement the agreement hammered out last Thursday in Geneva with Ukraine, the United States and the European Union.
Russia has lashed out at claims that it is dragging its feet on implementing the deal, laying the blame squarely on Kiev for violating the agreement.
The pact has been badly undermined by a deadly weekend shootout in Ukraine's restive east yesterday, and an obstinate refusal to stand down by pro-Kremlin militants who have seized control of nearly a dozen towns in the region.
The accord calls for all "illegal armed groups" in Ukraine to surrender their weapons and halt the occupation of public buildings and other sites.
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The White House said Biden -- who has emerged as the Obama administration's top pointman on the crisis -- would "consult on the latest developments in east Ukraine" during his trip, which comes amid the worst East-West crisis since the Cold War.
Today, he was due to speak with US embassy officials in the Ukrainian capital. Tomorrow he was to meet with the country's interim president, Oleksandr Turchynov, Prime Minister Arseniy Yatsenyuk and lawmakers.
Moscow though has cautioned that it will not tolerate further US sanctions if the deal falls apart, while stressing that it has tens of thousands of troops massed on Ukraine's doorstep.