Defying a protest ban, the energetic crowd chanted "Revolution!" and "Down with the gang" as it drove dozens of helmeted police off Kiev's iconic Independence Square. Protesters also steered a bulldozer within striking distance of metal barricades protecting the nearby presidential administration office.
AFP reporters saw security forces outside President Viktor Yanukovych's seat of power fire dozens of stun grenades and smoke bombs at masked demonstrators who were pelting police with stones and Molotov cocktails.
The economically struggling nation of 46 million was thrown into its deepest crisis since the 2004 pro-democracy Orange Revolution when Yanukovych snubbed EU leaders at a summit on Friday and opted to keep Ukraine aligned with its former master Russia.
EU leaders primarily blame the decision on the stinging economic punishments Russia had threatened should Ukraine take the fateful step toward the West.
Yet the move now threatens to backfire on Yanukovych as his political foes try to build momentum amid existing discontent with state corruption and disappearing jobs.
What the opposition describes as the largest Kiev protest since the 2004 uprising also saw a few dozen members of the nationalist Svoboda party take control of an empty Kiev city hall building.
The protesters hung a Ukrainian flag from the one of the building's windows and spray-painted a red sign reading "Revolution Headquarters" near its entrance.
"A revolution is starting in Ukraine," Svoboda party chief Oleh Tyagnybok declared.
"We are setting up a tent city on Independence Square... and launching a national strike," he said in dramatic scenes aired live on television stations in both Ukraine and Russia.
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