Petro Poroshenko made the announcement after discussions with Russian president Vladimir Putin by telephone.
Ukraine holds Moscow responsible for much of the violence in its east and has accused its neighbour of supplying arms and men to the rebels.
"The peace plan begins with my order for a unilateral ceasefire," said Mr Petroshenko. "I can say the period of the ceasefire will be rather short. We anticipate that, immediately after this, the disarming of the illegal military formations will take place."
Officials said the "temporary" ceasefire should be implemented "within hours or days" to provide pro-Russian separatists a chance to lay down their arms, and for any Russians involved to withdraw across the border. Those who do give up the fight will be granted an amnesty, but already one rebel group has rejected the ceasefire.
The announcement came as fighting between government and rebel forces continued.
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