After a meeting in Luxembourg, EU foreign ministers said they had decided to expand "the list of those subject to assets freezes and visa bans".
Earlier, UK Foreign Secretary William Hague had told reporters that he believed the seizure of official buildings in eastern Ukrainian towns and cities "is something that is being planned and brought about by Russia".
Moscow denies fomenting the unrest.
EU foreign ministers also approved measures to provide up to 1bn euros (£800m; $1.4bn) of economic assistance to Ukraine.
The ministers backed "the temporary reduction or elimination of customs duties" for Ukrainian exports to the EU.
In Washington, the US signed a $1bn loan guarantee agreement for Ukraine after a meeting between US Treasury Secretary Jacob Lew and his Ukrainian counterpart, Oleksandr Shlapak.
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