The Kiev offices of Ukrainian President Viktor Yanukovych are unguarded, with opposition protesters apparently in full control of the government district, say BBC correspondents.
The BBC's Kevin Bishop says he was able to walk straight into the courtyard.
Opposition leaders say President Yanukovych, whose whereabouts are unknown, must stand down immediately.
They have called for elections by 25 May - not by the end of December as envisaged in Friday's peace deal.
Despite the EU-mediated agreement signed on Friday, thousands of people have remained on the streets of Kiev.
Parliamentary speaker Volodymyr Rybak has resigned, citing ill health.
Vitaly Klitschko, leader of the opposition Udar party, told parliament as it met on Saturday: "We must, as the people demand, adopt a resolution calling on Yanukovych to immediately resign."
President Yanukovych is not in parliament - there are unconfirmed reports he has left Kiev, with suggestions that he has travelled to Kharkiv in the east, close to the Russian border.
On Thursday, police opened fire on protesters who have been occupying Independence Square in central Kiev. The health ministry said 77 people - both protesters and police - had been killed since Tuesday in the worst violence since protests began in November.
Our correspondent says there is no sign of security forces inside the previously heavily guarded presidential complex, though some government employees arrived for work.
Protesters are standing in the grounds of the building in disbelief, he adds.
One group of far-right protesters had threatened to take action if he did not resign by Saturday morning.
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