Neighbouring Poland closed its airspace near two southeastern cities and its air force scrambled jets in response until the danger had passed.
Ukraine's military early on Sunday said Russia had launched 595 drones and 48 missiles overnight and its air defences shot down 568 drones and 43 missiles. It noted that the main target of the strike was the capital Kyiv.
President Volodymyr Zelenskiy said the attack, which lasted more than 12 hours, killed four people, including a child, with two of the deaths occurring at a Kyiv cardiology clinic.
He said 80 people were injured in the strikes and factories, residential buildings and energy-generating sites were damaged.
Russia's defence ministry on Sunday said it had carried out a "massive" attack on Ukraine using long-range air- and sea-based weapons and drones to target military infrastructure, including airfields.
Moscow has denied targeting civilians in its war against Ukraine, although thousands have been killed and residential areas extensively damaged by its attacks.
Zelenskiy again urged the international community to act decisively to cut off Russia's energy revenues that fund its invasion. Ukraine has so far failed to convince US President Donald Trump to impose punitive sanctions on Moscow.
"The time for decisive action is long overdue, and we count on a strong response from the United States, Europe, the G7, and the G20," he said.
Speaking in his nightly video address, Zelenskiy said that while the UN was holding General Assembly sessions, Russia had "literally used every day, every hour, to strike at Ukraine. Vile strikes".
Zelenskiy said it was important that further sanctions on Russia to be adopted by Europe target Russia's energy resources, particularly its tanker fleet.
He described the overnight attack on the southeastern city of Zaporizhzhia as "extraordinarily fierce" with nearly 40 injured.
Kyiv awoke to loud explosions, drones flying overhead and air defences booming. Smoke from one of the strike sites drifted across the morning sky as the air raid alert ended at 9.13am, nearly seven hours after it began.
Reuters journalists visited an area in the suburbs of Kyiv, where rows of newly built homes were almost totally destroyed, and parked cars flattened by falling debris.
Residents sifted through the wreckage of an apartment block after their windows were blown in by the force of a blast.
Some people hurried to metro stations underground, from where they followed events on their mobile phones.
Attacks on such a scale have stretched Ukraine's limited air defences throughout 2025. Zelenskiy on Saturday said an additional Patriot missile system from Israel had been deployed and he expected two more to arrive this autumn.
He and other officials have asked international partners for more to protect Ukraine's skies, but air defence systems are limited in availability and other nations are keen to bolster their defences amid perceived threats from Russia.