But within two hours of the cease-fire's scheduled start, the warring sides were already trading accusations of fresh attacks.
International attention will be focused in the coming days on the strategic railway hub of Debaltseve, where Ukrainian government forces have for weeks been fending off severe onslaughts from pro-Russian separatists.
The US State Department said images from eastern Ukraine offer "credible pieces of evidence" that the Russian military has deployed larger amounts of artillery and multiple rocket launchers around Debaltseve to shell Ukrainian forces.
Ukrainian President Petro Poroshenko issued a cease-fire order in a live broadcast for all the country's armed forces to hold their fire from one minute after midnight Kiev time (2201 GMT, 5:01 pm EST).
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Accusations of violations were quick to follow. Ukrainian security services chief Valentyn Nalyvaichenko said one infringement was reported about 50 minutes after the deadline. Artillery salvoes were fired from an area that Nalyvaichenko said is under the control of a Cossack unit manned by Russian citizens.
Donetsk News Agency, a separatist mouthpiece, cited senior rebel defense official Eduard Basurin as saying the Ukrainian forces garrisoned in Debaltseve fired artillery and mortars at rebel positions.
"In the interests of preventing the death of the civilian population, precise fire is being deployed toward the enemy's positions," Basurin was cited as saying.
The hours before the cease-fire were marked by ferocious battles around Debaltseve, as Ukrainian armed forces undertook desperate attempts to gain control over a highway linking the town to their rearguard.
Speaking to his Russian counterpart Sergey Lavrov by telephone yesterday, US Secretary of State John Kerry expressed concern about what he called efforts by Russia and the separatists to cut off Debaltseve in advance of the cease-fire.