Biden said there would be “enormous consequences” for the world if Russia made a move on the nation, which sits on its southwestern border.
His comments came as other Western leaders repeated warnings that Russia would pay a heavy price for invasion.
Russia has accused the US and others of “escalating tensions” over the issue and denies it plans to enter Ukraine.
However, Moscow has built up troops at the border, with some 100,000 Russian soldiers deployed in the region.
Fielding questions from journalists, Biden replied “yes” when asked whether he could see himself imposing sanctions on the Russian president personally the event of an invasion.
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He said such a move across Ukraine’s border would mean “enormous consequences worldwide” and could amount to “the largest invasion since World War Two”.
Biden added that he would feel obliged to beef up NATO’s presence in eastern Europe.
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