According to officials, around 40 rockets were fired in two waves. Kyiv said two of them crossed NATO-member Romania's airspace on way to Ukraine.
The air raid alert sounded just before 8:30am Kyiv time and the all clear was given just before midday.
Air defenses were active across Ukraine, including in the Kyiv, Kharkiv, Odesa, Mykolaiv, Poltava, Dnipro, Lviv, Vinnitsya and Kirovohrad regions.
An explosion heard in Kyiv was the work of air defenses, offcials reported. Mayor Vitaliy Klitschko later said fragments from a rocket had damaged a car and the roof of a house.
Maksym Marchenko, regional governor of the southern region of Odesa, said: "Enemy aviation is in the air and ships which can carry Kaliber missiles are in the sea.
"The enemy launched the missiles. The air alert will be long. Please do not ignore the air alert sirens, and go to the shelters."
Russia also targeted "power plants and transmission system facilities," Ukrenergo said, adding that emergency power cuts have been put into place.
The number of missiles fired by Russia was smaller than previous mass-attacks, which have regularly involved 100+ missiles during its attempts to destroy Ukraine’s civilian energy infrastructure over the winter.
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The latest missile attack comes against a backdrop of ever-increasing concern over an expected renewed offensive from Russia.
An earlier air raid alert sounded across central and eastern Ukraine at around 4 a.m. on Friday morning.
Ukrainian air defenses shot down five Shahed drones and five Kalibr missiles launched by the Russians, Yurii Ihnat, spokesman for the Air Force of Ukraine reported.
He added that 35 S-300 missiles against which air defenses are not currently effective were launched at the Kharkiv and Zaporizhzhia regions.
In Kharkiv, "critical and infrastructure facilities were targeted" resulting in fires that were "quickly" put out, governor Oleg Sinegubov said.
He said nobody was injured but some parts of the city were without power. "Energy and industrial infrastructure" suffered damage in Zaporizhzhia, leaving sections of the city without electricity, local official Anatoly Kurtev said.
Kurtev said 17 strikes were recorded over the course of an hour, "the largest number" since Russia invaded nearly one year ago.
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