A further 24 people including Russian oligarchs and Ukrainian separatists have been slapped with travel bans and asset freezes under the sanctions, which have been delayed for the past week by disagreements between EU countries.
The sanctions come into force tomorrow, Van Rompuy said in a statement today, after sharp differences over whether their introduction might undercut peace efforts and with Moscow promising a forceful response.
Russia said today that it had already drawn up new anti-Western sanctions targeting imports of consumer goods and second-hand cars.
The 28 member states would then look at any such proposal "urgently", he said.
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"We have always stressed the reversibility and scalability of our restrictive measures," he said.
The sanctions coming into effect tomorrow are a toughening up of measures adopted in July after the shooting of Malaysia Airlines flight MH17 over rebel-held east Ukraine.
Under the latest round, the EU said three major Russian oil companies and three top defence companies would be barred from seeking debt financing from Europe.
EU nationals and companies are also barred from extending loans to the top five Russian state-owned banks.
They will also no longer be able to trade in the banks' bonds, shares or financial instruments with maturities of more than 30 days, a significant step up from the previous 90 days which could make it even more difficult for companies to raise fresh financing.
The move will likely make borrowing more expensive still for Russian companies, undermining an economy already in the doldrums.