The strikes hit as Ukraine was experiencing the coldest temperatures during the Russian invasion and damaged an iconic Soviet-era WWII monument.
They also came a day before Ukrainian and Russian negotiators were due to meet for a second round of talks in Abu Dhabi.
"Taking advantage of the coldest days of winter to terrorise people is more important to Russia than turning to diplomacy," Ukraine's President Volodymyr Zelensky said on social media, denouncing the attack.
AFP journalists heard explosions across the capital overnight and residents in over 1,000 buildings woke to find their heating cut off as temperatures dipped towards minus 20 Celsius.
The Kremlin had last week said it agreed to a US request not to strike Kyiv for seven days, ending Sunday.
Ukraine had not reported large-scale Russian attacks on the capital last week, while reporting continued attacks in other parts of the country.
"Several types of ballistic and cruise missiles, as well as drones, were used to strike high-rise buildings and thermal power plants," Energy Minister Denys Shmygal said.
"Hundreds of thousands of families, including children, were deliberately left without heat in the harshest winter frosts," he added.
Russia attacked with 71 missiles, as well as 450 attack drones, the Ukrainian air force said. Ukraine said it intercepted or destroyed 38 missiles and 412 drones.
Five people were wounded in the capital, officials said, adding that thousands were without electricity.
- 'Symbolic and cynical' -
The base of the city's towering Soviet-era Motherland statue was damaged.
"It is both symbolic and cynical: the aggressor state strikes at a place of remembrance of the struggle against aggression in the 20th century, repeating its crimes in the 21st century," Culture Minister Tetyana Berezhna wrote on social media.
Russian strikes had this month repeatedly cut power and heating to tens of thousands of homes -- with Kyiv and its European allies accusing Moscow of deliberately freezing Ukraine's population.
Strikes also hit Ukraine's second-largest city, Kharkiv, temporarily cutting heating to some 100,000 subscribers.
The hours-long attack targeted energy infrastructure and aimed to "cause maximum destruction... and leave the city without heat during severe frost", Kharkiv Governor Oleg Synegubov wrote on Telegram.
Authorities had to cut heating to more than 800 homes to prevent the wider network from freezing, he said, urging people to go to round-the-clock "invincibility points" around the city if they needed to warm up.
Overnight temperatures plunged to minus 19C in Kyiv and sank as low as minus 23C in Kharkiv.
- US-backed talks -
Washington has sought to craft a settlement between the two sides, but the first round of trilateral talks held in Abu Dhabi last weekend failed to yield a breakthrough.
A second round is due to begin on Wednesday in the Emirati capital.
Zelensky said on Monday that recent "de-escalation" with Russia was helping build trust in negotiations, apparently referring to a break in attacks on energy facilities.
The second round of talks is expected to focus on territory -- with no breakthrough so far on the crucial issue.
Russia wants full control of Ukraine's eastern Donetsk region, which Kyiv has ruled out, saying such a move would only embolden Moscow.
After failing in its aim of a lightning offensive to capture Kyiv and topple Ukraine's leadership in a matter of days in 2022, Russia has been bogged down in the face of Ukrainian defences and is now mounting a grinding advance that has come at huge human cost.
Moscow's troops accelerated their advance in Ukraine throughout January, capturing almost twice as much land as in the previous month, according to an AFP analysis.
Russia seized 481 square kilometres (186 square miles) in January, according to the analysis of data from the Institute for the Study of War, which works with the Critical Threats Project.
The January gains were up from 244 square kilometres in December 2025 and one of the largest advances during a winter month since Russia invaded four years ago.
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