Volodymyr Zelensky, 44, claimed he tried to contact Vladimir Putin, 69, after Russia recognised the independence of two regions in east Ukraine.
However, Mr Zelensky revealed the Russian President refused to respond.
He said: “Today I initiated a phone call with the President of the Russian Federation.
“The result was silence, though the silence should be in the Donbas.”
Mr Zelensky went on to issue a plea to the Russian people and warned steps taken by Mr Putin could lead to the “beginning of a big war”.
He said: “We are separated by more than 2,000km of mutual borders, along which 200,000 of your soldiers and 1,000 armoured vehicles are standing.
“Your leadership has approved their step forward onto the territory of another country.
“This step could become the beginning of a big war.”
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