Moscow responded by accusing its foes of seeking to derail a fragile ceasefire that came into force just a week ago, aimed at halting a conflict that has killed more than 2,700 people and inflicted heavy damage in towns and cities across Ukraine's industrial heartland.
While the guns have largely fallen silent after five months of fighting between Ukrainian forces and pro-Russian rebels, the rhetoric in the worst East-West crisis since the Cold War has just grown louder.
The fresh EU measures were also aimed at major Russian energy, finance and defence companies, including oil giant Rosneft and famed weapons manufacturer Kalashnikov.
The 28-member bloc also imposed asset freezes and visa bans on a host of Russian figures, including allies of President Vladimir Putin, as well as rebels in Ukraine and Crimea, a Ukrainian region that Russia annexed.
"These steps underscore the continued resolve of the international community against Russia's aggression," said US Treasury Secretary Jacob Lew.
But a dismissive Putin said the sanctions would have little effect and accused the West of using them as an "instrument to destabilise international relations".
EU nations finally approved the measures after deep divisions emerged in the wake of the ceasefire, with some worried about the effect on their own economies of any reprisals by Moscow.
Brussels has now agreed it could "amend, suspend or repeal" the measures after reviewing the truce at the end of September.
But European Commission head Jose Manuel Barroso, on a visit of solidarity to Kiev just as the sanctions took effect, chided Russia over its "unacceptable behaviour" in its Western neighbour.
In talks with President Petro Poroshenko, he described the ceasefire -- the first backed by both Kiev and Moscow since the conflict erupted in April -- as a positive step.
"However, it is still insufficient to guarantee sustainable peace," he added.
