Ukraine and Russia agreed a Türkiye-brokered deal last month to unblock Black Sea grain deliveries after Moscow's attack.
A UN-chartered vessel laden with grain has set off from Ukraine for Africa following a Türkiye-brokered deal to relieve a global food crisis.
The MV Brave Commander left the Black Sea port of Pivdennyi and will sail to Djibouti "for delivery to Ethiopia", the infrastructure ministry said on Telegram on Wednesday.
The ship is carrying 23,000 tonnes of wheat.
It is the first ship chartered by the UN World Food Programme (WFP) to leave Ukraine since the start of the Russian attack in February and the government has said it hopes two or three similar shipments will follow soon.
Ukraine and Russia are two of the world's biggest grain exporters.
Kiev and Moscow agreed a deal brokered by Türkiye and the UN last month to unblock Black Sea grain deliveries after Russia's attack.
The agreement lifted a Russian blockade of Ukraine's ports and established safe corridors through the naval mines laid by Kiev.
The Ukrainian port authority said that five boats in total with an overall cargo volume of 110,000 tonnes had left Ukraine Tuesday.
The first commercial ship carrying grain left on August 1. Since then, 21 ships have left Ukrainian ports, the port authority said in its statement.
The WFP says a record 345 million people in 82 countries face acute food insecurity and up to 50 million people in 45 countries are on the brink of famine and risk being tipped over the edge without humanitarian support.
"We are definitely planning other ships to leave the ports of Ukraine, to help people around the world," Marianne Ward, WFP deputy country director in Ukraine, told journalists earlier while the ship was being loaded at the weekend.
"This should just be the first of many humanitarian ships to leave the ports," she said.
Later Tuesday evening, the United States announced it would provide an additional $68 million to the WFP.
The funds will be used "to purchase, move, and store up to 150,000 metric tons of Ukrainian wheat to help respond to the global food crisis," said US Agency for International Development administrator Samantha Powers in a statement.