The first shipment carrying Ukrainian grain has set off from the port of Odesa on Monday morning.
The Sierra Leone-flagged cargo ship, Razoni, which has been loaded with corn, departed from the Black Sea port bound for Lebanon at 7.15am, a Ukrainian minister confirmed.
Other ships were also depart Ukraine's ports through the safe corridors in line with deals signed in Istanbul on July 22.
Russia and Ukraine signed separate agreements with Turkey and the U.N. clearing the way for Ukraine - one of the world's key breadbaskets - to export 22 million tons of grain and other agricultural goods that have been stuck in Black Sea ports because of Russia's invasion.
The deals also allow Russia to exports grain and fertilizers.
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09:02 AMUN chief welcomes grain update
Antonio Guterres, the secretary-general of the United Nation, "warmly welcomes" the departure of a first ship carrying Ukrainian grain under a plan to lift Russia's naval blockade, a spokesman said on Monday.
"The Secretary-General hopes that this will be the first of many commercial ships moving in accordance with the initiative signed, and that this will bring much-needed stability and relief to global food security, especially in the most fragile humanitarian contexts," the UN said in a statement.