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The UK will "respond decisively" to Russia's "unprovoked attack" on Ukraine, Boris Johnson has said.
The PM said he was "appalled" after President Putin launched a military operation in the eastern Donbas region.
Mr Putin said he did not plan to occupy Ukraine, but Ukraine has branded it a "full-scale invasion".
The PM will chair a Cobra meeting at 07:30 GMT to discuss the "horrific attacks".
In a phone call with the Ukrainian President Volodymyr Zelensky in the early hours of Thursday morning, Mr Johnson said the people of Ukraine were in the UK's thoughts "during this time", a No 10 spokesperson said.
The prime minister told Mr Zelensky the West "would not stand by as President Putin waged his campaign against the Ukrainian people".
In a tweet, Foreign Secretary Liz Truss said the UK stood with Ukraine and would work with international partners to respond to Russia's "terrible act of aggression".
It comes after President Putin announced a "special military operation" in Ukraine's Donbas region in a televised address to the Russian people on Thursday morning.
He said the Ukrainian people would be able "to choose freely" who ran the country.
Mr Putin urged Ukrainian soldiers in the combat zone in eastern Ukraine to lay down their weapons and return to their homes, and warned that Moscow's response would be "instant" if anyone tried to take on Russia.