Ukraine said Wednesday Russia fired a missile at a civilian ship entering a port in the Black Sea region of Odesa, injuring the ship's crew and killing a harbour pilot.

Since a UN-brokered deal guaranteeing safe passage for civilian ships collapsed in July, both Kyiv and Moscow have ramped up military activity and attacks in the Black Sea.

"Continuing the terror of civilian shipping, the enemy insidiously fired an Kh-31P anti-radar missile in the direction of one of the ports of Odesa region from tactical aircraft in the Black Sea," the Ukrainian army said.

"The missile hit the structure of a civilian vessel flying the Liberian flag as it was entering the port," it added.

It said a harbour pilot was killed, while another port worker was injured.

"Three crew members, citizens of the Philippines, were injured, one of them was hospitalised," it added.

The collapse of the UN-backed grain export deal in July prompted Moscow to warn that any ships entering Ukrainian ports could be viewed as potential military targets.

Ukraine subsequently announced the launch of a new "humanitarian corridor" -- a sea route for civilian ships -- that avoids international waters.

But Russia has continued to attack Ukraine's grain-exporting ports and infrastructure.