It follows a vote by parliament to release her after President Viktor Yanukovych fled the capital Kiev.
Speaking after her release, the Ukrainian opposition leader said “the dictatorship has fallen”.
Yulia Tymoshenko was sentenced to seven years in jail in 2011 after a controversial verdict on her actions as prime minister.
The glamorous, fiery orator who helped lead the Orange Revolution – Ukraine’s revolt against a controversial election in 2004 – was convicted of criminally exceeding her powers when she agreed a gas deal with Russia which was seen to have disadvantaged her own country.
Yulia Tymoshenko has always insisted the charges were untrue, inspired by Viktor Yanukovych, the man she helped oust in 2004 who returned to defeat her in the 2010 presidential election.
The EU had demanded her release as one of the conditions of the EU-Ukraine trade pact that President Viktor Yanukovych rejected last year – triggering the protests that led to the current crisis.
Olha Lappo, spokeswoman for the Fatherland party Yulia Tymoshenko leads, said she was heading from prison in the eastern city of Kharkiv to the capital Kiev to join protesters there.
Yulia Tymoshenko’s release was made possible by a European-brokered peace deal between her President Viktor Yanukovych and the opposition on Friday.
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