FSB director Alexander Bortnikov and Mikhail Fradkov, a former prime minister who now heads the foreign intelligence service, were among 15 Russians or Ukrainians and 18 companies and other organisations named in the EU's latest sanctions list.
Read MoreRussian central bank surprises with rate hike
Also sanctioned were the secretary of Russia's Security Council, Nikolai Patrushev, Chechen leader Ramzan Kadyrov, who the EU said had made statements supporting Russia's annexation of Ukraine's Crimea region and the insurgency in eastern Ukraine, and several Ukrainian separatist leaders.
After months of hesitation, the EU is set to go beyond asset freezes by imposing sanctions on sectors of the Russian economy.
The 28-nation EU toughened its stance towards Moscow following last week's downing of a Malaysian airliner, killing 298 people, in an area of eastern Ukraine held by Russian-backed separatists.
EU ambassadors reached a preliminary agreement on Friday.
European Council President Herman Van Rompuy wrote to EU leaders asking them to authorise their ambassadors to complete an agreement by Tuesday. That would avoid the need for leaders to hold a special summit to approve the sanctions.
Van Rompuy said the proposed sanctions package "strikes the right balance" in terms of costs and benefits to the EU and in its flexibility to ramp up sanctions or reverse them over time.
"It should have a strong impact on Russia's economy while keeping a moderate effect on EU economies," he wrote in the letter, seen by Reuters.
Read MoreUkraine: What's the next big disruption?
But Van Rompuy said the sanctions on access to capitalmarkets, arms and hi-tech goods were likely to apply only to future contracts, leaving France free to go ahead with the controversial delivery of Mistral helicopter carriers being built for Russia.
The narrowing of the proposed measures highlighted the difficulty of agreeing to tough sanctions among countries which have widely different economic interests and rely to varying degrees on Russian gas.
European Commission President Jose Manuel Barroso said late on Friday that following the ambassador's discussions the Commission had adopted a draft legal text for the Russia sanctions package.
"The final decision now lies with the EU's member states, but I believe that this is an effective, well-targeted and balanced package providing the flexibility to adjust our reaction to changes on the ground. I hope that member states will agree on this package of restrictive measures next week," he said in a statement.