Poroshenko, on a visit to Australia, spoke as a day-old ceasefire largely held along the bloodied frontline in eastern Ukraine, but hopes of peace talks and pulling back heavy weaponry still hung in the balance.
"Please stop the fire. Please release the hostages. Please withdraw your troops from my territory," Poroshenko said in a joint press conference with Australian Prime Minister Tony Abbott.
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Residents in the main rebel stronghold of Donetsk experienced an unfamiliar silence overnight as both Ukrainian and rebel forces called off shelling.
"It was quiet for the first time in two months," said 26-year-old Oksana Leventova, who lives in Donetsk.
"It was disconcerting, but my kids slept peacefully."
Interviews with people along the frontline confirmed the ceasefire -- the fourth since the separatist war broke out in April -- was being largely respected.
But there were still enough minor violations for the Ukrainian military to delay withdrawal of heavy weaponry from the frontline and the creation of a buffer zone.
"For the first time in a long time in east Ukraine, the military did not suffer any losses (on Tuesday)," said military spokesman Andriy Lysenko, but he added there had been 16 shots fired.
"Once there has been a day without a single shot, it will signal we can start the process of withdrawing heavy weapons," he said.
The fate of peace talks -- which the government had initially hoped to convene in the Belarussian capital Minsk on Tuesday -- was also uncertain.
Poroshenko said Russia must abide by a peace plan agreed in Minsk on September 5 that was meant to establish a 30-kilometre buffer between the fighters and grant limited self-rule to the separatists.
But hostilities only intensified after the two rebel regions -- the self-proclaimed People's Republics of Lugansk and Donetsk -- held their own leadership polls on November 2 that were denounced by both Kiev and the West.
Rebel leader Andrei Purgin yesterday said that the two sides were still discussing a date and agenda for talks, and expected them to go ahead tomorrow.
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