KIEV, Ukraine – More than 100,000 people took to the streets of Kiev on Sunday, and thousands more rallied in other cities across Ukraine, to demand the resignation of President Viktor Yanukovych, the largest outpouring of fury so far over his refusal to sign far-reaching political and trade accords with the European Union.

Speakers at the rally in Kiev said that protests — now in their 11th day — would continue until Yanukovych was toppled and new elections were called.

"I want the authorities to know that this is not a protest, this is a revolution!" said Yuri V. Lutsenko, a former ­interior minister and a leader of Ukraine's Orange Revolution in 2004, speaking to the huge crowd that thronged Independence Square in defiance of a court order. "Revolution!" the crowd roared back. ­"Revolution!"

With the public's anger deepened by the brutal force used by the police to disperse protesters in Kiev early ­Saturday, fissures have emerged at the highest levels of Yanukovych's administration, as well as in Parliament.

Serhiy Lyovochkin, the chief of the presidential administration staff, reportedly submitted his resignation Friday.

At least five lawmakers from Yanukovych's Party of Regions, which controls Parliament, spoke out forcefully against the violence by the police, and at least two, David Zhvania and Inna Bohoslovska, said they had quit the party.

Bohoslovska sent a text message to one of the protest leaders, Yegor Sobolev, telling him: "If I can be useful, I am here. Let's go to the rally."

Many Ukrainians view the agreements with Europe as crucial to a brighter economic and political future and to breaking free, once and for all, from the grip of Russia and Ukraine's Soviet past. The steady escalation of the protests — and the violent crackdown — has created a volatile situation.

More violence erupted late Sunday afternoon outside the presidential administration building when demonstrators clashed with a battalion of police officers guarding the building. Smoke bombs and stun grenades were set off, and the police responded with tear gas.

Authorities reported Sunday night that about 100 police officers and more than 50 protesters had been injured, including some with chemical burns to their eyes from tear gas. The police made scattered arrests but did not immediately release a tally.

There also were signs that some of Ukraine's wealthiest business leaders, the so-called oligarchs, were turning against Yanukovych or at least positioning themselves for a potentially big shift in the ­government.

Yanukovych also was the antihero of the Orange ­Revolution in 2004, when mass protests erupted in response to blatant election fraud that led to his comfortable victory over Viktor Yushchenko in contradiction to exit polls and preliminary returns. The protests led to a new election, which Yushchenko won.

Yanukovych made a comeback in 2010, when he defeated Yulia Tymoshenko, the former prime minister, who has since been convicted of abuse of authority and imprisoned.

The government drew heavy global criticism, including from the United States.