Beyond the 13 people, two enterprises were also added to the list by the 28 EU ministers, according to two officials who spoke on condition of anonymity because the measure had yet to be officially announced.
The EU had previously ordered visa bans and asset freezes for 48 people, but it is the first time it includes businesses on the list.
After today's addition a total of 61 people are included on the EU list.
Beyond the visa and asset measures, British Foreign Secretary William Hague said that it is essential to show Moscow the bloc is ready to step up measures further "depending on Russia's attitude toward the elections" in Ukraine.
He joined other ministers at the foreign ministers meeting in Brussels in dismissing yesterday's referendums in parts of eastern Ukraine as shams of democracy, saying "they are illegal by anybody's standards."
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