One person has died and five more were left injured as Kyiv came under fire from Russian troops for the first time in three weeks.
The missile strikes, rained down on a kindergarten in the capital city early this morning before rescue crews pulled women and children, including a seven year old girl, from the rubble.
It is the first attack by warmongerer Vladimir Putin's forces on Kyiv since June 5.
Several blasts rang through the city at around 6.30am as fire crews battled flames and rescued civilians from a nine-storey apartment building in the central Shevchenkivskiy district.
Debris was strewn over parked cars outside a smouldering building with a crater in its roof while a private kindergarten had smashed windows and a large blast crater by a playground about 400 metres away, Reuters said.
"They (rescuers) have pulled out a seven-year-old girl. She is alive. Now they're trying to rescue her mother," Kyiv's mayor Vitali Klitschko said.
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"There are people under the rubble," Klitschko said on the Telegram messaging app.
He added that several people had already been hospitalised.
Some privately-held storage garages in the area were also completely destroyed.
It comes after the people of Kyiv had experienced relative quiet during the last three weeks, while the war raged on in the east.
Head of the regional military administration, Oleksiy Kuleba, said Ukraine troops had successfully shot down one missile.
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He branded the Russian attack as an attempt by Putin to intimidate Kyiv ahead of G7 and NATO summits this week.
Russian troops had moved from Kyiv and concentrated on the Donbas region in the east of Ukraine, where a fierce battle over the strategic city of Severodonetsk has raged on.
Ukrainian troops finally pulled out yesterday but despite this progress, Putin has reportedly sacked his top general leading the battle.
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The allegedly dismissed General Alexander Dvornikov, who is reported to be a drunk and distrusted by his officers, would be another telling sign of Putin's frustration with his war in Ukraine which he once believed he would conquer in four days.
Russian high command is thought to have removed a number of high-ranking officers from key command roles in Ukraine since the start of June, according to the British Ministry of Defence.
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With Dvornikov the commander of Southern Group of Forces and likely acting as the overall operational commander for the Russian army in Ukraine, his removal is reported to have come along with that of Airborne Forces (VDV) General-Colonel Andrei Serdyukov, MailOnline said.
But Dvornikov's rumoured replacement, Colonel-General Sergei Surovikin has been condemned by the MoD as an allegedly corrupt and brutal military man.
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It said: "For over 30 years, Surovikin's career has been dogged with allegations of corruption and brutality."
In southern Ukraine along the Black Sea coast, nine missiles fired from Crimea hit the port city of Mykolaiv on Saturday, the Ukrainian military said.
In the north, about 20 missiles were fired from Belarus into the Chernihiv region.
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Ukraine's military intelligence agency said the Russian bombers' use of Belarusian airspace for the first time during Saturday's attack was 'directly connected to attempts by the Kremlin to drag Belarus into the war'.
Belarus hosts Russian military units and was used as a staging ground before Russia invaded Ukraine, but its own troops have not crossed the border.
Ukrainian President Volodymyr Zelensky said that as a war that Moscow expected to last five days moved into its fifth month, Russia 'felt compelled to stage such a missile show'.
He said: "When we know that the enemy will not succeed, when we understand that we can defend our country, but we don't know how long it will take, how many more attacks, losses and efforts there will be before we can see that victory is already on our horizon."
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After their success capturing the heavily contested port city of Severodonetsk, Russian troops are now looking to secure the rest of the Donbas region in the east by blocking the city of Lysychansk from the south.
Russian defence ministry spokesman Igor Konashenkov said late on Saturday that Russian and Moscow-backed separatist forces now control Severodonetsk and the villages surrounding it.
Ukrainian resistance had been blocked with troops retreating after weeks of bombardment and house to house fighting.
Capturing Lysychansk would give Russian forces control of every major settlement in the province, while they already control around half of Donetsk, the second province in Donbas.
The population of Severodonetsk has been decimated from 100,000 to just 10,000 during weeks of fighting, with most of the city reduced to rubble.