The barrage - the latest in almost-daily, widescale attacks - included aerial glide bombs that have become part of a fierce Russian onslaught in the three-year war.
The intensity of the Russian attacks on Ukraine in the past weeks has further dampened hopes that the warring sides could reach a peace deal anytime soon - especially after Kyiv recently embarrassed the Kremlin with a surprising drone attack on military airfields deep inside Russia.
According to Ukraine's Air Force, Russia struck with 215 missiles and drones overnight on Saturday, and Ukrainian air defences shot down and neutralised 87 drones and seven missiles.
Several other areas in Ukraine were also hit, including the regions of Donetsk, Dnipropetrovsk, Odesa, and the city of Ternopil, Ukrainian Foreign Minister Andrii Sybiha said in a post on X.
"To put an end to Russia's killing and destruction, more pressure on Moscow is required, as are more steps to strengthen Ukraine," he said.
The Russian Defence Ministry on Saturday said its forces carried out a night-time strike on Ukrainian military targets, including ammunition depots, drone assembly workshops, and weaponry repair stations.
There was no comment from Moscow on the reports of casualties in Kharkiv.
Kharkiv's mayor, Ihor Terekhov, said the strikes also damaged 18 apartment buildings and 13 private homes.
Terekhov said it was "the most powerful attack" on the city since Russia's full-scale invasion of Ukraine in February 2022.
Kharkiv's regional governor, Oleh Syniehubov, said two districts in the city were struck with three missiles, five aerial glide bombs and 48 drones.
He said two children, a baby boy and a 14-year-old girl, were among the injured.
In the Dnipropetrovsk province further south, two women aged 45 and 88 were injured, according to local Governor Serhii Lysak.
Russian shelling also killed a couple in their 50s in the southern city of Kherson, close to the front lines, local Governor Oleksandr Prokudin reported in a Facebook post.
Meanwhile, Russia's defence ministry said its forces shot down 36 Ukrainian drones overnight, over the country's south and west, including near the capital.
Drone debris injured two civilians in the suburbs of Moscow, local Governor Andrei Vorobyov reported.
On Friday, Russia struck six Ukrainian territories, killing at least six people and injuring about 80.
Among the dead were three emergency responders in Kyiv, one person in Lutsk and two people in Chernihiv.
A US-led diplomatic push for a settlement has brought two rounds of direct peace talks between delegations from Russia and Ukraine, although the negotiations delivered no significant breakthroughs.
The sides remain far apart on their terms for an end to the fighting.
Ukraine has offered an unconditional 30-day ceasefire and a meeting between its President Volodymyr Zelenskiy and Russian leader Vladimir Putin to break the deadlock.
But the Kremlin has effectively rejected a truce and hasn't budged from its demands.
US President Donald Trump said this week that Putin told him Moscow would respond to Ukraine's attack on Russian military airfields last Sunday.
Trump also said it might be better to let Ukraine and Russia "fight for a while" before pulling them apart and pursuing peace.
Trump's comments were a remarkable detour from his often-stated appeals to stop the war and signalled he might be giving up on recent peace efforts.
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