The overnight attacks followed a warning from Russian President Vladimir Putin, conveyed via US President Donald Trump, that the Kremlin would hit back after Ukrainian drones destroyed several strategic bomber aircraft in attacks deep inside Russia.
Kyiv's military administration said those killed in the missile and drone salvo were first responders who had rushed to the scene of one of the strikes, Interior Minister Ihor Klymenko said.
"Overnight, Russia 'responded' to its destroyed aircraft... by attacking civilians in Ukraine.... Multi-storey buildings hit. Energy infrastructure damaged," Foreign Minister Andrii Sybiha wrote on X.
Russia's Defence Ministry said its forces had carried out the strike on military and military-related targets in response to what it called Ukrainian "terrorist acts" against Russia.
President Volodymyr Zelenskiy said 49 people across Ukraine had been injured in the attacks, which also struck several other towns and cities as well as Kyiv, as he called on Ukraine's Western allies to ramp up pressure on Russia.
"If someone is not applying pressure and is giving the war more time to take lives - that is complicity and accountability. We must act decisively," he wrote on X.
The city's metro transport system was disrupted by a Russian strike that hit and damaged tracks between stations, Kyiv's military administration said.
Ukraine's state rail company Ukrzaliznytsia said it was also detouring some trains due to railway damage in the region.
In the Solomianskyi district, a Russian drone slammed into the side of apartment building, leaving a gaping hole and burn marks, a Reuters photographer at the scene said.
Falling concrete blocks from the building crushed cars parked below. Two police investigators were examining what appeared to be the drone's engine.
Earlier in the night, Reuters reporters heard the sound of Russian kamikaze drones buzzing in the sky, accompanied by the sounds of outgoing fire from Ukrainian anti-aircraft fire.
Witnesses reported a series of booming explosions powerful enough to rattle windows far from the impact sites.
Some Kyiv residents sought shelter in metro stations, or in underground car parks.
As well as Kyiv, Russian forces also struck industrial facilities and infrastructure in the western city of Ternopil, leaving parts of it without power, Mayor Serhii Nadal said.
The regional administration said the attack had injured 10 people and recommended that residents temporarily stay inside due to a high concentration of toxic substances in the air after a fire.
Fifteen people were injured in the northwestern city of Lutsk where an attack damaged private homes, educational institutions and a government building, prosecutors said.
In one of the most audacious attacks of the war between Ukraine and Russia, Ukrainian spies last weekend destroyed some of Russia's strategic bomber aircraft on the ground using quadrocopter drones hidden in wooden sheds.
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