Pro-Western Ukrainians are planning to blockade the seat of government in Kiev, in the hopes of forcing authorities to sign an historic pact with the EU.
The move comes a day after tens of thousands of demonstrators swarmed the centre of the capital to protest a shock decision to scrap plans to sign an agreement that would have deepened ties with the European Union.
It marked the biggest rally in the country since the 2004 Orange Revolution overturned a rigged presidential poll and forced a new ballot that saw the former Soviet republic elect a pro-Western president.
Waving flags, letting off smoke bombs and shouting "revolution" some protesters on Sunday attempted to storm the government headquarters but were forced back with police batons and tear gas.
The opposition set up tents on European Square in central Kiev and vowed to remain there until President Viktor Yanukovych signs a broad political and trade agreement with the EU at a summit in Vilnius this week.
On Monday, the opposition was expected to put forward fresh demands for the government to hold an emergency meeting.
Some 500 people had gathered on the square by mid morning.
Last week the government unexpectedly announced it was halting all preparations to sign an Association Agreement with the EU at the Vilnius summit this week, a deal which would have marked a historic break from the Kremlin.
The government decision came after the Ukrainian parliament failed to adopt legislation that would have freed jailed opposition leader Yulia Tymoshenko, a key EU condition for Ukraine to sign the agreement.
The government cited "national security" for its decision, but faced accusations from the West that it had caved into pressure from Moscow.
In turn Russian President Vladimir Putin, who has repeatedly threatened Ukraine with retaliation if Kiev signed the deal, accused the EU of "blackmailing" Ukraine.
The Kremlin wants Ukraine to be part of its Customs Union which also includes ex-Soviet Belarus and Kazakshtan.
Linguistic and historic fault lines divide Ukraine into the Kremlin-friendly Russian-speaking east and the fervently nationalistic Ukrainian-speaking west, and Yanukovych's decision to put the negotiations with the EU on ice is expected to once again polarise the nation.
While many pro-Western Ukrainians protested the government's decision on Sunday, others took to the streets to defend Ukraine's ties with historical master Russia.
Police put attendance at the main rally on Sunday at 23,000 people. The opposition gave a higher estimate, saying more than 100,000 turned out.
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