Petro Poroshenko's initiative follows his announcement on Friday of a week-long unilateral ceasefire in the government's 10-week "anti-terrorism" campaign in the industrial east that has claimed more than 375 lives and displaced tens of thousands of people.
The hostilities raged yesterday despite the oder as federal forces used artillery fire to repel waves of raids by militias who rejected the terms of his pact.
And it also received only a lukewarm endorsement yesterday from Russian President Vladimir Putin.
The 48-year-old confectionery tycoon - elected on May 25 in snap polls called after month of deadly pro-EU protests toppled Kiev's Kremlin-backed president in February - said that a peaceful settlement was "our plan A".
More From This Section
"But those who are planning to use peaceful negotiations only to buy time and regroup their forces must know that we have a detailed plan B. I am not going to speak of it now because I believe that our peaceful plan will work out," he added in the 12-minute address.
But Putin took the extra step yesterday to call on "the conflicting parties to halt all military activities and sit down at the negotiating table" - a comment that implied a degree of criticism for the rebels' continued attacks.
Today Poroshenko opened the door to talks, saying that the "immediate fulfilment of the peaceful plan will open the path to the political dialogue."
"I am ready to talk with those who have erred, who mistakenly stood in the position of separatism," he added.
Poroshenko said parliament would soon draft a bill granting amnesty "to those members of illegal armed formations who did not kill civilians and Ukrainian soldiers.