The EU’s latest measures target 12 people involved in Russia’s annexation of Crimea.
Earlier, Ukraine and the EU signed an accord forging closer political ties.
Separately, the Organization for Security and Co-operation in Europe (OSCE) has agreed to send monitors to Ukraine, after Russia dropped objections.
The six-month mission will initially consist of 100 international civilian monitors, who will be employed in nine regions of Ukraine – including the south-eastern areas rocked by violence between pro-Ukraine and pro-Russian activists.
The observers will not go to Crimea but German Foreign Minister Frank-Walter Steinmeier said the decision was “a step that helps to support our de-escalation efforts”.
Western diplomats had blamed Russia for several failed attempt to agree such a mission to help defuse the tense situation.
In Brussels, EU leaders also said they would step up efforts to reduce energy dependency on Russia.
The EU’s new sanctions add to an existing list of 21 officials affected by travel bans and asset freezes.
They include Deputy PM Dmitry Rogozin and two close aides of Vladimir Putin, Sergei Glazyev and Vladislav Surkov.
The speakers of Russia’s two houses of parliament, Valentina Matviyenko and Sergei Naryshkin – both at Vladimir Putin’s side as he signed the Crimea law – are also included.
While the list targets several figures close to the Russian president, it does not hit his inner circle as hard as the sanctions announced by the US on Thursday.
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