A burnt-out line of buses and trucks in central Kiev marks the boundary between protesters and police.
Clashes erupted on Sunday, after many more demonstrators rallied peacefully against President Viktor Yanukovych.
The authorities say police have the right to use firearms in self-defense.
In a statement on Monday evening, President Viktor Yanukovych said that “now, when peaceful actions are turning into mass unrest, accompanied by riots and arson attacks, the use of violence, I am convinced that such phenomena are a threat not only to Kiev but to the whole of Ukraine”.
Last week the president’s supporters in the Ukrainian parliament gave police extra powers to tackle demonstrators.
At least 20 people have been arrested in the clashes, and about 100 injured, including dozens of police officers.
The violence followed weeks of mainly peaceful action against Kiev’s decision to spurn a political agreement with the EU, and then to toughen anti-protest laws.
Viktor Yanukovych says he is now ready to negotiate with pro-EU protesters and opposition leaders.
A cross-party commission was being set up on Monday to try to resolve the deepening crisis.
Former Interior Minister Yuriy Lutsenko, who was injured in clashes earlier this month, is among four representatives of the opposition who will be taking part in the talks with the authorities, according to the website for Ukraine’s Fatherland Party.
On the road leading from Europe Square to parliament, riot police were still standing behind shields on Monday, lined up against dozens of protesters who had camped out overnight despite temperatures dropping well below freezing.
The police are firing plastic bullets, tear gas canisters and stun grenades, and even throwing back the cobblestones, he reports.
EU foreign ministers also released a statement on Monday expressing “deep concern” about the new legislation, which they said was passed under “doubtful procedural circumstances”.
“These legislative acts would significantly restrict the Ukrainian citizens’ fundamental rights of association, media and the press, and seriously curtail the activities of civil society organizations,” they said, following a monthly meeting.
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