The decision brings the total number of people on an EU sanctions blacklist to 72, with two firms in Crimea also subject to an asset freeze, an EU statement said.
"In view of the gravity of the situation in eastern Ukraine, the Council has today expanded the list of persons subject to targeted sanctions for actions undermining Ukraine's territorial integrity," it added.
The EU declined to name those concerned, whose identities will be released in the EU Official Journal on Saturday when the sanctions enter into force.
EU diplomats told AFP however that the majority were Ukrainians, with some holding dual Ukraine-Russia nationality, and were relatively "small fry".
There were sharp divisions this week between members of the 28-nation bloc over the list, with some nations – notably Britain, Latvia, Lithuania, Poland and Sweden – calling for sanctions against higher-level officials.
"Some of us questioned whether this was an adequate response," said a diplomat from one of the five nations, speaking on condition of anonymity.
EU leaders late last month had demanded Russia change tack on Ukraine or face the prospect of tougher sanctions.
The EU has so far balked at outright sanctions on economic sectors despite strong pressure from Washington.
