Explosions shook central Kyiv and reverberated across the capital in the early hours of Thursday as thousands of residents rushed to bomb shelters and underground metro stations.
Huge columns of smoke filled the skyline.
The death toll climbed to 30 after three more bodies were recovered from the rubble, Ukraine's emergency service said, with the toll likely to rise further.
The head of the capital's military administration, Tymur Tkachenko, earlier said 91 were injured.
About 130 buildings were damaged, with the scale and spread of destruction across the capital having little precedent even in a war now in its fifth year.
Twenty-four people died in an attack on Kyiv in May.
President Volodymyr Zelenskiy, who cut short his visit to Ireland and rushed home, visited the site where a nine-storey residential building was half-destroyed.
He blamed the destruction in part on a failure of allies to deliver promised air defences.
"If our partners had delivered on their promises in a timely manner, I think we could have saved more homes and lives today," said Zelenskiy, who looked tired and frustrated.
"All we ask of our partners is simply to do what we've agreed on. We're not even asking for more."
Later, in his nightly video address, Zelenskiy said the issue of air defences would be "one of the key outcomes" of next week's NATO summit in Turkey, as he repeated his call for the development of European air defences.
"If, of course, NATO still means anything to the allies," he said.
"Europe must have its own sufficient capability to defend against all types of threats, including this one - from Russian ballistic missiles."
Russia launched 74 missiles and 496 drones overnight, the Ukrainian air force said, adding the number of ballistic missiles was unusually high and the interception rate was low.
Ukraine has struggled with shortages of Patriot missiles in recent months.
The Russian defence ministry, in a Telegram post, said its "massive attack" using long-range, high-precision air-, land- and sea-launched weapons and drones hit military and energy facilities, as well as airports in Kyiv and other locations.
Moscow said the attacks were retaliation for Ukrainian drone strikes on Russia.
Kyiv, which has stepped up strikes in recent weeks on Russia's domestic fuel supply, said it had hit an oil refinery on Thursday in the Russian region of Nizhny Novgorod, where the governor reported one person killed in a strike on an industrial facility.
The Kremlin said Russian military commanders had briefed President Vladimir Putin about the Russian attacks, adding that Moscow would increase pressure to achieve its war aims.
Kyiv Mayor Vitali Klitschko announced a day of mourning in Kyiv for Friday.
He said that damage was recorded across the city of about three million, with some buildings heavily damaged.
After years of enduring relentless long-range attacks from Russia, Ukraine has intensified its own strikes deep into Russian territory, mainly on energy targets.
That has triggered a fuel crisis in Russia, forcing the world's third-biggest oil producer to import petrol from as far away as India.
Russia has responded with a stepped-up air campaign against Ukrainian cities, in June hitting a 1000-year-old Kyiv cathedral foundational to the Orthodox faith in both countries.
Kaja Kallas, the EU's foreign policy chief, said only sustained military support for Ukraine and increased pressure on Moscow could help stop Russian attacks.
"Today, I will propose to sanction more entities supporting Russia's military-industrial complex in response to the strikes," she said in a post on X.
"The more Moscow attacks civilians, the more sanctions must be imposed."
with Reuters
