The attack raised new doubts about the viability of the deal, which was intended to release about 20m tonnes of grain to ward off famine in parts of the developing world.
In one of the largest attacks on the city since the war began, the airstrikes rattled buildings in the city centre and sent up a plume of smoke that was visible across the city.
On Odesa's seafront, beachgoers applauded as the city's air defences brought down two of four missiles, the remaining two hitting the port.
The attack on Odesa was one of a series of Russian strikes across Ukraine, with the city of Kropyvnytsky being hit by 13 missiles.
The new attacks came hours after Moscow and Kyiv signed deals with the UN and Turkey to avert a global food crisis and supposedly clear the way for the shipment of millions of tonnes of Ukrainian grain and some Russian grain and fertiliser held up by the war.
Spared so far from Russian invasion and the direct artillery attacks that have struck Ukraine's other coastal cities, Odesa is still threatened by rockets from submarines and strategic bombers, while its busy port has been strangled until now by the Russian naval blockade.
Once one of Russia's principal military objectives, the cosmopolitan port city with its pastel buildings and streets lined with horse chestnut, mulberry and white acacia is in limbo.
"Ideologically, Putin views Odesa as the heart of his 'Novorossiya' strategy," wrote Christine Karelska for the Visegrad/Insight website last week.
"He is entrapped by the illusion that Odesa's residents are waiting for the Russian occupiers to 'liberate' them.
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