The attack late Tuesday came as Ukraine endorsed an American proposal for a 30-day ceasefire and agreed to immediate negotiations with Russia.
Ukrainian officials said the attack occurred as the ship was being loaded with a grain consignment intended to be sent to Algeria.
"Unfortunately, four people died -- citizens of Syria. The youngest victim was 18, the oldest was 24 years old. Two more people were wounded -- a Ukrainian and a Syrian," Oleksiy Kuleba, vice prime minister for reconstruction, wrote on social media.
"Russia is attacking Ukraine's infrastructure, including ports that are involved in ensuring the world's food security," he added.
Separately, the governor of the Dnipropetrovsk region said a 47-year-old woman was killed during a Russian missile attack on the central city of Kryvyi Rig, the hometown of President Volodymyr Zelensky.
The Ukrainian air force said that in total Russia had launched three missiles at the war-battered country overnight as well as 133 drones of various types, including the Iranian-designed Shahed-type attack drone.
Ukrainian air defence units shot down 98 of the drones, the air force added.
Prosecutors in the eastern Ukrainian region of Donetsk, which the Kremlin claims is part of Russia, said separately that three people had been killed and two wounded in Russian strikes.
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