According to a statement released by the EU foreign ministers, targeted sanctions including asset freezes and visa bans would be introduced “as a matter of urgency”.
At least 21 anti-government protesters died in clashes in Kiev on Thursday.
Officials said that one policeman had also died and that 67 police had been captured by protesters.
“No circumstances can justify the repression we are currently witnessing,” the statement from EU foreign ministers said.
EU foreign policy chief Catherine Ashton said the “prime responsibility” to get talks between the two sides under way lay with President Viktor Yanukovych.
Speaking after an emergency meeting of EU foreign minsters in Brussels, Catherine Ashton said ministers had expressed their “dismay” at the latest violence and had agreed to “suspend export licences for equipment for internal repression”.
Implementation of the measures “will be taken forward in light of developments in Ukraine”, she added.
The EU has until now refrained from imposing sanctions on Ukraine, preferring to emphasise dialogue and compromise.
The US state department had already announced visa bans on 20 members of the Ukrainian government but has not provided any names.
At least 21 protesters were killed by security forces in Kiev on Thursday following the breakdown of a truce the previous day. Officials say 67 people have now died in violence since Tuesday.
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