Ukraine has intercepted 31 missiles launched by Russia at Kyiv overnight, Ukraine's air force said.
At least 17 people, including a child, were injured by falling debris, four of whom are in hospital, authorities said.
It is the largest Russian attack in weeks and follows a vow from Moscow for revenge over recent attacks by Ukraine on its border regions.
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The attack prompted Ukraine's President Volodymyr Zelensky to renew his call for more military aid from Western allies.
Several explosions were heard throughout Kyiv shortly before dawn as its anti-missile defence systems shot the rockets down.
Debris fell in the Podilsky, Shevchenkivskyi and Sviatoshyn districts, causing fires on the roofs of a power transformer, several residential buildings and cars, the head of the city military administration Serhiy Popko said on Telegram.
He added that some windows had been blown out in the shockwaves.
"As a result of successful combat operations, all enemy missiles were shot down over Kyiv and on the approaches to the capital," Mr Popko posted on Telegram.
Kyiv residents described chaos as debris rained down on them.
"The cars were burning over there, everything was exploding... I came back, took cat carriers, tried to find my cats, but I couldn't," said one, Tetiana.
On Wednesday, five people were killed in a Russian attack in Kharkiv, Mr Zelensky said.
Earlier this week, authorities in the nearby Sumy region said that more than 150 people had been forced to flee because of intensified shelling.
Mr Zelensky has repeated his calls for further military aid over recent days, specifically calling on the West to send Ukraine more air defence systems.
"Such terror continues every day and night. World unity can stop it when it helps us with air defence systems," Mr Zelensky said in a post on Telegram, hours after the Kyiv attack.
"Now this protection is needed here in Ukraine... It is quite possible if the partners have enough political will," he said.
Last month, Mr Zelensky made an urgent appeal for more weapons at an international conference in Germany.
"Keeping Ukraine in the artificial deficits of weapons, particularly in a deficit of artillery and long-range capabilities, allows Putin to adapt to the current intensity of the war," he said.
On the other side of the border, Russian towns have also been hit by attacks
Earlier this week, 16 people were killed and 98 were injured in a series of attacks on the Russian border city of Belgorod, governor Vyacheslav Gladkov said.
Thousands of children will be evacuated from the city and the surrounding area over the coming weeks as a result, he added.
Last week, Russian President Vladimir Putin said that the Ukrainian strikes on Russia "do not and will not go unpunished."
In Brussels, EU leaders are meeting to discuss boosting military and financial aid for Ukraine. A proposal to transfer billions of euros' worth of frozen Russian assets to Kyiv may also be discussed.
In a letter sent to leaders ahead of the summit, European Council President Charles Michel wrote that the bloc was facing a "pivotal moment" and that the summit would be a chance to "accelerate" the EU's efforts to send military aid to Ukraine.
Mr Michel also wrote that the EU needed to put its economy on a "war footing".
