The UK and EU are sanctioning 178 people, targeting those propping up the Russian-backed separatist areas of eastern Ukraine.
Six family members and close associates of Russian oligarchs are among those singled out.
The import of Russian iron and steel has also been banned from Thursday.
Meanwhile, ‘quantum technologies and advanced materials that Putin sorely needs’ will no longer be able to be exported.
It comes as Ukrainians in the east are warned to flee ahead of an expected huge Russian offensive that ‘could be decisive’.
Foreign Secretary Liz Truss said: ‘In the wake of horrific rocket attacks on civilians in eastern Ukraine, we are today sanctioning those who prop up the illegal breakaway regions and are complicit in atrocities against the Ukrainian people.
‘We will continue to target all those who aid and abet Putin’s war.
‘From tomorrow, we are banning the import of Russian iron and steel, as well as the export of quantum technologies and advanced materials that Putin sorely needs.
‘We will not rest in our mission to stop Putin’s war machine in its tracks.’
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