The clashes, the worst in Kiev in recent times, came amid mounting anger over new restrictions on protests ordered by President Viktor Yanukovych after almost two months of protests over his refusal to sign a pact for integration with the EU.
A special commission set up by Yanukovych was due today to meet representatives of the opposition for emergency talks but it was unclear if this could in any way help ease the crisis.
The White House urged an end to the violence, with US National Security Council spokeswoman Caitlin Hayden saying that Washington was deeply concerned and urging "all sides to immediately de-escalate the situation".
The spokeswoman warned that Washington was still considering sanctions against Ukrainian officials, a step urged by the Ukrainian opposition.
"The US will continue to consider additional steps - including sanctions - in response to the use of violence."
However, the situation remained tense with protesters launching occasional sorties at the police line to throw stones or Molotov cocktails.
After a peaceful mass rally in the afternoon, hundreds of demonstrators sought to storm police cordons near the Verkhovna Rada parliament and close to the stadium of the legendary Dynamo Kiev football club in central Kiev, witnesses and AFP correspondents said.
Their faces covered by scarves or ski masks, many of the protesters wielded sticks or even chains. Later in the night, they began to dig the cobble stones out of the road to hurl at police and use as barricades.
The security forces made extensive use of water cannon in a bid to douse the protesters and push them back and used rubber bullets which activists said left dozens injured.
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