"In light of events, we decided to expand the list of those subject to asset freezes and visa bans," EU foreign affairs head Catherine Ashton said.
Already, 33 Ukrainian and Russian officials and business leaders, including members of Russian President Vladimir Putin's inner circle, have been targeted.
EU ministers held Russia responsible for the latest developments in eastern Ukraine where pro-Kremlin militias continued to occupy many government buildings in defiance of a Kiev ultimatum to leave or face the consequences.
The 28 foreign inisters also demanded that Russia "call back its troops from the Ukrainian border and immediately withdraw the mandate of the Federation Council to use force on Ukrainian soil".
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Going into the meeting, Britain and France had sought a tough response.
"Further sanctions have to be the response to Russia's behaviour," British Foreign Secretary William Hague said, describing developments in eastern Ukraine as "clearly a further escalation of the crisis".
Ashton gave no details of who might be added to the EU sanctions list and said only that officials were working on it.
Current sanctions stop short of outright economic measures, which come under a third phase of action the EU agreed earlier this year and this option was noted again in today's statement.
Ministers noted that "any further steps by (Russia) to destabilise the situation in Ukraine would lead to additional and far reaching consquences for relations in a broad range of economic areas".