Vladimir Putin has ordered that Russia’s nuclear deterrence forces are put on high alert.
Mr Putin said aggressive statements by NATO leaders and economic sanctions against Moscow were behind the decision.
Speaking on state television on Sunday, he said: “As you can see, not only do Western countries take unfriendly measures against our country in the economic dimension – illegitimate sanctions that everyone knows about.
“But also the highest-ranking officials of leading NATO countries are allowing themselves to make aggressive statements in relation to our country.
“For this reason I order the minister of defence and the chief of general staff to put deterrent forces on special combat duty.”
The move will heighten fears across the West that Russian forces could use nuclear weapons in the conflict with Ukraine.
Sky News Moscow correspondent Diana Magnay described the decision as an “incredibly dramatic, escalatory move”, which will “really, really worry people”.
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“This is the first time that we’ve ever had a situation, in Putin’s reign at least, where he has put his nuclear forces ready essentially for combat duty, on high alert,” she said.
It comes after Ukrainians spent a third night largely underground sheltering from Russian forces following the initial invasion on Thursday.