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A ship carrying grain has left the Ukrainian port of Odessa for Lebanon under a safe passage agreement, the first departure since the Russian invasion blocked shipping through the Black Sea five months ago.
Ukraine's foreign minister called it "a day of relief for the world", especially for countries threatened by food shortages and hunger because of the disrupted shipments.
The sailing was made possible after Turkey and the United Nations brokered a grain-and-fertiliser export agreement between Russia and Ukraine last month.
"The first grain ship since #RussianAggression has left port," Infrastructure Minister Oleksandr Kubrakov wrote on Twitter.
"Today Ukraine, together with its partners, makes another step to prevent world hunger."
The Turkish defence minister said earlier the Sierra Leone-flagged ship Razoni would head to Lebanon.
The Russian invasion of Ukraine on February 24 has led to a worldwide food and energy crisis, with the United Nations warning of the risk of multiple famines this year.
Russia and Ukraine account for nearly a third of global wheat exports. But Western sanctions on Russia, coupled with fighting along Ukraine's eastern seaboard, have prevented grain ships safely leaving ports.
The deal aims to allow safe passage for grain shipments in and out of Odessa, Chornomorsk and the port of Pivdennyi.
Ukrainian Foreign Minister Dmytro Kuleba said on Twitter: "The day of relief for the world, especially for our friends in the Middle East, Asia, and Africa, as the first Ukrainian grain leaves Odessa after months of Russian blockade".
Moscow has denied responsibility for the food crisis, blaming Western sanctions for slowing exports and Ukraine for mining the approaches to its own ports.
Turkish Defence Minister Hulusi Akar said the Razoni would anchor in the Bosphorus off Istanbul on Tuesday afternoon and will be inspected by a joint team of Russian, Ukrainian, United Nations and Turkish representatives.
"It will then continue as long as no problems arise," he said.
Ukrainian presidential officials have said 17 ships are docked in Black Sea ports with almost 600,000 tonnes of cargo, mostly grain.
Kubrakov said more ships would follow. Unlocking the ports would provide at least $US1 billion ($A1.4 billion) in foreign exchange revenue for Ukraine's economy and allow the agricultural sector to plan next year's sowing season, he said.
Despite the breakthrough on the grain shipments, the war ground on elsewhere.
Three civilians were killed by Russian shelling in the Donetsk region - two in Bakhmut and one in nearby Soledar - in the last 24 hours, regional governor Pavlo Kyrylenko said.
An important industrial city and transport hub, Bakhmut has been under Russian bombardment for the past week as the Kremlin's forces try to occupy all of Donetsk.
It is connected by road to the towns of Lysychansk and Sievierodonetsk in Luhansk region, which is almost all occupied by Russia.
Luhansk governor Serhiy Gaidai said the road was crucial for delivering weapons to Ukrainians fighting in Sievierodonetsk and evacuating people from that area.
Russian strikes also hit Kharkiv - Ukraine's second biggest city and situated near the border with Russia - on Monday, regional governor Oleh Synegubov said.
After failing to quickly capture the capital Kyiv early in the war, Russia has turned its forces on Ukraine's east and south and has been aiming to capture the Donbas region, made up of Donetsk and Luhansk.
Ukrainian President Volodymyr Zelenskiy said Russia has been transferring some forces from the Donbas to the southern Kherson and Zaporizhizhya regions.
Russia annexed Crimea in 2014 and Kyiv says Moscow is seeking to do the same with the Donbas and link it to Crimea in the south.
Russian missiles on Sunday pounded Mykolaiv, a port city on the River Bug estuary off the Black Sea that borders the mostly Russian-occupied Kherson region.
Mykolaiv Mayor Oleksandr Senkevych said more than 12 missile strikes - probably the most powerful on the city in five months of war - hit homes and schools, with two people confirmed killed and three wounded.
Ukrainian grain tycoon Oleksiy Vadatursky, founder and owner of agriculture company Nibulon, and his wife were killed in their home, Mykolaiv Governor Vitaliy Kim said.