The attacks came as Washington and Seoul echoed warnings from Ukraine that North Korean troops had begun "engaging in combat operations" alongside Russian forces on the border between the warring countries.
Ukraine's air force said its units had downed four missiles and 37 drones launched by Russia over eight regions of Ukraine overnight and into Wednesday morning.
"It is important that our forces have the means to defend the country from Russian terror," President Volodymyr Zelensky said in response to the attack.
Ukraine has for months been appealing to its Western allies to provide more air-defence systems to fend off Russian attacks on cities and critical infrastructure.
The large-scale bombardment comes at a critical moment on the battlefield. Russian forces are advancing in the east and concerns are growing over future aid for Ukraine after Donald Trump's victory in US presidential elections.
AFP journalists heard explosions ring out over Kyiv and saw dozens of residents seeking shelter in an underground metro station in the centre of the capital.
Kyiv officials said one man was wounded by falling debris from a downed drone in the suburb of Brovary, while emergency services distributed images of firefighters battling flames at one impact site.
A separate drone attack in the Ukrainian-controlled southern region of Kherson, which the Kremlin claims is part of Russia, killed a 52-year-old woman, the regional head said.
- 'Missile approaching' -
Multiple air raid sirens rang out early Wednesday as authorities said missiles were closing in on Kyiv, which was home to nearly three million people before Russia invaded in February 2022.
"As missiles were approaching Kyiv, the enemy simultaneously launched a ballistic missile attack on the capital. The enemy attack ended with another drone strike," city authorities said.
The attack is the latest in an uptick in escalating strikes on Ukrainian cities, mainly in the south of the war-battered country.
A Russian strike this week on Kryvyi Rig, Zelensky's hometown, killed a 32-year-old mother and her three children.
The Kremlin has repeatedly denied its forces target civilians in Ukraine, a claim its spokesman repeated Wednesday in response to a question over whether Russian forces were working to minimise civilian casualties.
Over the weekend, Moscow and Kyiv launched record overnight drone attacks on each other.
Ukraine's Foreign Minister Andriy Sybiga held a meeting with US Secretary of State Antony Blinken in Brussels, where he stressed the need for more air defence systems after the latest night attack.
He also urged a strong response to the deployment of North Korean troops as Russia tries to push out Ukrainian forces out of its Kursk border region.
"Russia is using Iranian drones, North Korean ballistic missiles and troops to attack Ukraine. In response, the Kremlin is providing assistance to these regimes," Sybiga said.
- 'Injected into battle' -
South Korea's spy agency said North Korean soldiers were "engaging in combat" in Kursk after US officials confirmed Pyongyang's troops were actively fighting for Moscow against Ukraine.
Blinken said earlier he had discussed North Korea's actions with NATO chief Mark Rutte, saying Pyongyang's troops had been "injected into the battle, and now, quite literally, in combat."
That development "demands, and will get, a firm response," he pledged.
Kyiv has warned that Russia has amassed a force of 50,000 troops -- including North Korean soldiers -- to push out Ukrainian forces from the Russian border region of Kursk.
At the same time, Russian ground forces have been making rapid advances in Ukraine's eastern Donetsk region, which the Kremlin claims is part of Russia.
On Wednesday, the Russian defence ministry said its troops had wrested control of the village of Rivnopil, where an estimated 98 people lived before the invasion.
To face both the North Korean threat and the continued Russian assaults, Ukraine has been advocating for allies to allow it to use long-range weapons deep inside Russian territory.
Moscow repeated warnings against the move.
"The response to the use of Western long-range systems on the territory of our country would be inevitable and devastating," said Foreign Ministry spokeswoman Maria Zakharova.
Separately, a source in the Security Service of Ukraine said the agency had orchestrated a car bomb attack in Crimea -- the Ukrainian peninsula annexed by Russia in 2014 -- that killed senior Russian naval officer Valery Trankovsky.
burs-brw/jc/giv
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