AFP journalists on the scene saw bodies covered by blankets strewn on the street, while images from officials showed exhausted emergency service workers smeared with blood and dirt dousing flames and treating wounded colleagues.
Local authorities said Russian aerial bombardments struck residential buildings, ambulances and a gas pipeline, leaving at least 20 people dead and wounding another 73 people, including rescuers.
Maria Slyzovska, who witnessed the attack, said the first strike rocked her mother's home leaving "everything broken" before the second missile hit.
"There were a lot of people there. There was blood and ambulances. We all live in the realities of this Russian roulette," she told AFP.
Zelensky said Russian forces had launched a type of attack known as a double-tap strike on the port hub, with the second projectile ploughing into rescue workers at the scene.
City officials said Moscow targeted Odesa with Iskander missiles launched from the Crimean peninsula, annexed by Russia in 2014.
"Russian terror in Odesa is a sign of weakness of the enemy, which is fighting Ukrainian civilians at a time when it cannot guarantee security for people on its own territory," said presidential aide Andriy Yermak.
- Kyiv, Moscow exchange barrages -
There was no immediate comment on the strikes from Russia, whose forces have routinely targeted the transport hub with drones and missiles.
The strikes came on the first day of presidential elections in Russia, which is also hosting the vote in several occupied regions of Ukraine, angering Kyiv.
UN Secretary-General Antonio Guterres as well as more than 50 member states slammed Moscow for holding the vote in parts of Ukraine, with Guterres saying that the "attempted illegal annexation" of those regions has "no validity" under international law, according to spokesman Stephane Dujarric.
Russian deputy UN ambassador Dmitry Polyanskiy said he would not comment on criticisms regarding "the domestic affairs of our country."
Friday's attack was just the latest in a series of fatal barrages between Kyiv and Moscow, as polls opened across Russia.
Kyiv said that a Russian drone strike killed two people in the central Ukrainian region of Vinnytsia, and that shelling on the frontline Zaporizhzhia region killed one woman.
National police said that Russia had attacked the Vinnytsia region, more than 400 kilometres (250 miles) from the frontlines, with drones, leaving a 52-year-old man and his 53-year-old wife dead.
In the southern Zaporizhzhia region, which Moscow claims to have annexed and partially controls, a 76-year-old woman was killed when fragments of a Russian shell hit her in her garden, Ukrainian Governor Ivan Fedorov said.
- 'Trying to break through' -
Moscow-installed officials in the Russian-held city of Donetsk meanwhile said a "barbaric" Ukrainian attack on a residential area had killed three children.
"Three children died. A girl born in 2007, a girl born in 2021, and a boy born in 2014," Alexey Kulemzin, the Russian-appointed mayor of Donetsk, wrote on Telegram.
Russia also said Ukraine launched drone and artillery attacks on areas closer to the countries' shared border.
The governor of Russia's Belgorod region, Vyacheslav Gladkov, said in a post on Telegram: "The town of Grayvoron came under Ukrainian army shelling."
"There is a dead man. He is a member of our territorial self-defence unit," he said.
Gladkov later added another man had been killed and two more injured by shrapnel in shelling of Belgorod city.
The uptick in attacks on Russia's border regions come after its forces last month captured the city of Avdiivka, just a few kilometres north of Donetsk.
It said pushing Ukrainian forces back would help protect residents of areas under its control from shelling.
The head of Ukraine's army said Friday that Russia had launched a wave of attacks to try to advance further in the area.
"The enemy has concentrated its main efforts and has been trying to break through ... for several days in a row," Ukrainian commander-in-chief Oleksandr Syrsky said in a statement after visiting front lines around Avdiivka.
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