The BBC's Daniel Sandford in Kiev says ''wave upon wave'' of attacks have been carried out on the police line
Clashes have been taking place after large crowds of pro-EU demonstrators rallied in Ukraine's capital against new laws restricting public protests.
Stun grenades and flares were thrown as groups of people tried to get to the parliament, their way blocked by rows of police and buses.
Opposition politician Vitali Klitschko tried to stop attacks on police.
The laws were passed with a quick show of hands on Thursday by MPs loyal to President Viktor Yanukovych.
The opposition accused the ruling party of a coup.
US and EU officials have expressed deep concern at the new legislation.
Ukraine's current anti-government movement began in protest at Mr Yanukovych's decision in late November to pull out of a landmark treaty with the EU, but has expanded to demand his resignation.
'Extremists and provocateurs'
Sunday's rally in Kiev, attended by tens of thousands, heard calls from opposition politicians to disregard the new laws curbing protests that pro-EU demonstrators have been staging for the past two months.
Clashes erupted as some people headed away from the main square towards parliament, to vent their anger over the new laws. They ran into police cordons.
They pelted police with flares, thunder flashes and petrol bombs, the BBC's Daniel Sandford in Kiev reports.
They overturned a bus used by police and set it alight. Other vehicles were also set on fire. One vehicle was pushed towards the police lines.
Police could be seen behind buses sheltering under their riot shields, and occasionally throwing their own thunder flashes and gas canisters to try to force the crowd back, our correspondent says.
The stand-off was continuing after darkness fell.
Some in the crowd of protesters attacked a bus being used by the police as a cordon
It was set alight after petrol bombs were thrown
Opposition leader Vitaly Klitschko (centre), who called for calm, was sprayed with a powder fire extinguisher
Interior ministry spokesman Serhiy Burlakov blamed "provocateurs and extremists" for the confrontations and urged people not to follow their lead.
Police were filming everything and had opened criminal proceedings under Article 294 (organisation of mass riots), the interior ministry said.
Call for defiance
Earlier the rally on the main square heard a call from a former Ukrainian navy chief for members of the armed forces to defy "illegal" orders from those in power, Unian news agency reported.
Rear Adm Ihor Tenyukh, who was sacked by President Yanukovych in 2010, warned of the dangers posed by the "coup d'etat planned by the current authorities".
"Tomorrow the regime will enslave you too. Therefore we are calling on you to fulfil your military oath of loyalty to the Ukrainian people and not to the authorities who have gone off the rails," he was quoted as saying.
Some demonstrators wore masks, also in defiance of the new law
Kiev has seen protest rallies every Sunday for two months
Former Ukrainian Foreign Minister Borys Tarasyuk (second from left) was among those taking the stage
Opposition leaders are under huge pressure to come up with an action plan, amid criticism from many activists that their campaign has been too passive.
The new curbs on protests, which have been signed into law by the president, include:
- A ban on the unauthorised installation of tents, stages or amplifiers in public places
- Provision to arrest protesters wearing masks or helmets
- A ban on protests involving more than five vehicles in convoy
- Hefty fines or jail for breaches of law
The protesters have been camping out behind extensive barricades on the Euromaidan, as Independence Square has been dubbed, for nearly two months.
The mass demonstrations were initially triggered by President Yanukovych's last-minute rejection of an EU deal under heavy pressure from Russia in November.
The protesters' demands later widened to include the fight against what they said was widespread government corruption and abuse of power.
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