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Poroshenko appealed for US and EU help to secure his crisis-torn country's porous border with Russia and stem the influx of arms and militants into the conflict zone.
Ukraine's new Western-backed president announced plans Wednesday to order a unilateral ceasefire in the separatist east that could help end a bloody pro-Russian insurgency and avert his ex-Soviet country's breakup.
Petro Poroshenko took a further step toward relieving tensions with Russia by deciding to replace acting Foreign Minister Andriy Deshchytsya — a hate figure in Moscow — with his current envoy to ongoing OSCE-mediated negotiations with the Kremlin.
But he also appealed for US and EU help to secure his crisis-torn country's porous border with Russia and stem the influx of arms and militants into the conflict zone.
More from GlobalPost: Ukrainian president calls for unilateral ceasefire
The frontier has witnessed ferocious clashes in recent weeks in which militants armed with Russian-made rocket launchers attack federal border guard camps and ambush Ukrainian army patrols.
A Ukrainian defense spokesman said the rebels had recently "stepped up their activities" and killed three soldiers while wounding eight in the industrial region of Lugansk.
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Poroshenko unveiled his peace initiative after late-night talks with Vladimir Putin in which the Kremlin chief also raised concern about the death in Lugansk fighting on Tuesday of two members of a Russian state TV crew.
"The peace plan begins with my order for a unilateral ceasefire," Poroshenko told reporters in Kyiv.
"Immediately after that, we must receive support for the presidential peace plan from all sides involved (in the conflict). This should happen very shortly."
Ukraine's acting Defense Minister Mykhailo Koval said the order would be issued "literally within days."
Poroshenko's peace plan also calls for Putin to formally recognise the new leadership in Ukraine that rose to power following the ouster of a pro-Russian administration in February after months of pro-EU protests.
Russia's first reaction to Poroshenko's announcement was guarded.
"On the one hand, they are talking about a ceasefire. And on the other, they are continuing their aggression," Russian Foreign Minister Sergei Lavrov said.
The 48-year-old confectionery tycoon won Ukraine's May 25 presidential election on a promise to quickly end the country's worst crisis since its independence from the Soviet Union in 1991.
Yet Poroshenko's problems have since been compounded by a cut in Russian gas supplies that threatens to plunge the country into an even deeper recession and erode his public support.
Poroshenko said the ceasefire was meant to be a temporary measure to give the militants a chance to disarm.
The rebels have previously rejected similar calls and vowed to continue a campaign to join Russia that a UN report said has killed at least 356 civilians and fighters on both sides.
A top commander in the self-proclaimed Donetsk People's Republic dismissed Poroshenko's idea as "meaningless."
"We are only interested in seeing the occupying forces leave our land," Denis Pushilin told Moscow's Dozhd television.
Poroshenko's decision to tap 46-year-old Pavlo Klimkin to replace Deshchytsya as foreign minister will help address one of the biggest irritants in relations with Moscow.
Klimkin is a veteran diplomat who recently served as Ukraine's ambassador to Germany and is now Poroshenko's personal representative at talks with Moscow that were launched on June 8 by the Vienna-based Organization for Security and Cooperation in Europe (OSCE).
Deshchytsya became embroiled in controversy at the weekend when he called Putin "a prick" while trying to restrain protesters who attacked Moscow's embassy compound in Kyiv.
Lavrov responded by saying that he had no intention of speaking to Deshchytsya again.
Ukraine's parliament is largely expected to approve Klimkin's candidacy in a vote due later this week.
Poroshenko's talks with Putin and nomination as foreign minister of a figure who has already won a degree of trust from Moscow come in sharp contrast to the freeze in relations that followed Russia's annexation of Crimea in March.
But the new leader has also stressed that he will be unable to put an end to the fighting until Ukraine regains complete control of its 2,000-kilometer (1,230-mile) land border with Russia.
The US State Department on Tuesday once again expressed concern about "the movement of military tanks and other equipment across the border" into eastern Ukraine.
Poroshenko's office said he told German Chancellor Angela Merkel by telephone on Tuesday that Western help sealing the frontier was "essential."
The United States has pledged "non-lethal military aid" such as helmets and medical supplies for Ukraine's underfunded armed forces.
But Washington has refused to provide any combat equipment and rejects the idea of deploying ground forces in Ukraine.