The EU on Thursday slapped an asset freeze and travel ban on 12 more Russians and Ukrainians following Moscow's annexation of Crimea, bringing to 33 the number of figures targeted by the European bloc.
Russian soldiers patrol the area surrounding the Ukrainian military unit in Perevalnoye, outside Simferopol, on March 20, 2014
French President Francois Hollande announced the measure after a meeting of European Union heads of state and government gathered to discuss the Ukraine crisis for the second time in less than two weeks.
"Russia must understand that it cannot continue, that it must take the path of dialogue," Hollande said.
The names of those targeted will be made public on Friday.
The EU move came on the heels of an announcement by US President Barack Obama of a new round of punitive measures against 20 Russian lawmakers and senior government officials, in addition to 11 individuals already targeted.
Russia has retaliated by issuing its own list of sanctions against nine US officials, including senior political figures and aides to Obama.
Hollande said earlier that "borders cannot be redrawn and a region allowed to pass from one nation to another without a response".