The 28 EU ministers also said in a statement yesterday that two firms in Russia-annexed Crimea would be hit with asset freezes later monday.
The ministers agreed to expand the scope of visa bans and asset freezes to target people undermining stability in Ukraine or obstructing international organisations there.
The Obama administration has its own sanctions list that targets several close associates of Russian President Vladimir Putin and their assets for Russia's actions in Ukraine.
The targets of the new sanctions include Russia's top prosecutor in Crimea; the commander of Russian airborne troops; a member of Putin's staff, and people identified by the EU as leaders of the armed pro-Moscow revolt in eastern Ukraine.
A total of 61 people are now on the EU's sanctions list due to Ukraine.
The two companies sanctioned, Chernomorneftgaz and Fedosia, have been effectively confiscated by the new leaders in Crimea following a resolution by the pro-Russian local parliament that proclaimed the appropriation of their assets, the EU said.
France and Germany had already called on Russia to promote de-escalation in Ukraine so its presidential elections could take place May 25.
If there is no action from President Vladimir Putin, the EU could increase sanctions, the two nations said.
The EU threw its weight behind efforts of the Organisation for Security and Cooperation in Europe set up talks in Ukraine to contain the chaos and violence.
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