"We now have the most far-reaching sanctions ever - depleting Russia's war arsenal and biting deep into its economy," European Commission chief Ursula von der Leyen said on Twitter, adding the bloc was turning up the pressure on those trying to circumvent EU sanctions.
EU foreign policy chief Josep Borrell warned the bloc would continue to pile more sanctions on Moscow.
"We will continue to increase pressure on Russia - and we will do it for as long as needed, until Ukraine is liberated from the brutal Russian aggression," he said in a statement.
Borrell said the latest sanctions tackled the banking sector, Moscow's access to technology that can be used for civilian and military purposes and advanced technologies.
The package adds electronic components used in Russian weapons systems retrieved on the battlefield, including drones, missiles, helicopters, as well as specific rare earth materials, electronic integrated circuits, and thermal cameras to the list of banned exports.
It also imposes tighter export restrictions on another 96 entities for supporting Russia's military and industrial complex, including for the first time seven Iranian entities manufacturing military drones used by Moscow.
Additional restrictions are imposed on imports of goods which generate significant revenues for Russia, such as asphalt and synthetic rubber.
Ukraine's President Volodymyr Zelenskiy and Prime Minister Denys Shmyhal urged the EU on Saturday to keep increasing the costs for Russia of its invasion.
"The pressure on Russian aggressor must increase. We expect decisive steps against [Russia's state-owned nuclear energy company) Rosatom & Russian nuclear industry, more pressure on military & banking," Zelenskiy tweeted.
"We expect further intensification of pressure and restrictions, especially in the area of the nuclear industry and the activities of Rosatom," Shmyhal said in tweet.
EU member states agreed on the sanctions late on Friday after hectic last-minute haggling, after Poland temporarily threw a spanner into the works.
Warsaw said the proposed restrictions on EU imports of Russian rubber included such a big quota of imports exempted and such long transition periods that they would have no effect in practice.
Other EU countries were baffled that Warsaw - a leading Russia hawk in the bloc - was risking having no new sanctions announced on the key anniversary over a single element of a broader package.
All member states need to approve sanctions for them to be enacted, making negotiations among the 27 often tedious and lengthy.
(Reporting by Sabine Siebold; Additional reporting by Dan Peleschuk in Kyiv; Editing by Mike Harrison)