The four bulk carriers were loaded with almost 170,000 tonnes of corn and other foodstuffs, Ukraine's sea ports authority said on Facebook.
The resumption of grain exports is being overseen by a Joint Coordination Centre (JCC) in Istanbul where Russian, Ukrainian,Turkish and U.N. personnel are working.
The United Nations and Turkey brokered the deal last month after U.N. warnings of possible outbreaks of famine in parts of the world due to a halt in grain shipments from Ukraine that had squeezed supplies and sent prices soaring.
On Saturday, a foreign-flagged ship arrived in Ukraine for the first time since the war started in February to be loaded with grain, Infrastructure Minister Oleksandr Kubrakov said.
"We are gradually moving on to larger volumes of work. We plan to ensure the ability of the ports to handle at least 100 vessels per month in the near future," he said on Facebook on Sunday.
Before Russia's invasion of Ukraine, Russia and Ukraine together accounted for nearly a third of global wheat exports.
The first ship to leave a Ukrainian port under the deal will not arrive in Lebanon on Sunday as planned, the Ukrainian embassy in Lebanon said. The Razoni left Odesa last Monday carrying 26,527 tonnes of corn.
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Sources: Reuters