The European Union closed all its airspace to Russian aircraft, seek to ban Russian state-owned media in the bloc and target Russian ally Belarus with sanctions, European Commission President Ursula von der Leyen said on Sunday.
The banning of Russian state-owned media would include outlets Sputnik and Russia Today (RT).
Von der Leyen also said that the EU would for the first time finance the purchase and delivery of weapons and other equipment to Ukraine.
"This is a watershed moment for our Union," she said in a short delivered statement.
British Foreign Minister Liz Truss said on Sunday there could be no talks with Russia over Ukraine while Moscow has troops in its neighbor, adding that the conflict could be protracted.
"Now if the Russians are serious about negotiations they need to remove their troops from Ukraine. They cannot negotiate with a gun to the head of the Ukrainians ... So frankly, I don't trust these so-called efforts of negotiation," she told Sky News.
"I've compiled a hit list of oligarchs ... We are working through putting the cases together and every few weeks we will sanction new oligarchs. There will be a rolling program of sanctions ...There will be nowhere to hide," she added.
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But she said that sanctions would take time to degrade not only the Russian economy but also its "war machine."
"This could be a number of years because what we do know is Russia has strong forces and we know that the Ukrainians are brave and they are determined to stand up for their sovereignty and territorial integrity."
Other Western nations announced new sanctions on Russia on Sunday, including blacklisting its banks and banning technology exports.
One of the biggest results in Ukrainian President Volodymyr Zelensky's eyes was the limited disconnection of SWIFT from some Russian institutions. They have so far stopped short of forcing Russia out of the SWIFT system for international bank payments, though Germany's foreign and economic ministers and French presidential official indicated on Saturday that such a move may come soon.
"Our diplomats fought around the clock and with inspiration for all European countries to agree on a strong and fair decision to disconnect Russia from the international interbank network. We also have this victory. This is billions and billions of losses for Russia - a concrete price for this vile invasion of our state," Zelensky said on Saturday night.
Earlier, Canada, Spain and Portugal on Sunday announced that their airspaces are closed to Russian planes and airline operators.
A string of European countries including Britain, Germany and Italy have already taken the same measure in response to the invasion of Ukraine.
Air France AIRF.PA has also decided to stop all operations from and to Russia, the company said on Sunday.
"In light of the situation in the region, Air France has decided to suspend flights to and from Russia as well as the overflight of Russian airspace until further notice as from 27 February," its statement said.
The decision will also lead to flights to and from countries such as China and Japan being called off while Air France is studying alternative routes, the statement added.
Turkish Foreign Minister Mevlut Cavusoglu said on Sunday it was implementing an international pact on naval passage to the Black Sea.
Under the 1936 Montreux Convention, Turkey has control over the Dardanelles and Bosphorus straits that connect the Mediterranean and Black seas and can limit the passage of warships during wartime or if threatened.
Cavusoglu made the comment in a live interview with broadcaster CNN Turk. Turkey earlier called Russia's invasion of Ukraine a "war" on Sunday in a rhetorical shift that opened the way for the move.
Von der Leyen said that sanctions would be applied to Belarusians helping the Russian war effort. The EU will also extend on Belarus the same export restrictions on dual-use goods for Russia.
FedEx and UPS have also suspended operations in Russia, according to the Wall Street Journal.