Around 100 supporters on Tuesday surrounded a police van in Kiev and broke free a stateless former Georgian president turned Ukrainian governor who had been arrested at his house on allegations of trying to overthrow the government.

Mikheil Saakashvili, who has been stripped of his Georgian and Ukrainian citizenship, recently forced his way back across the border into Ukraine where he leads an anti-government protest movement against President Petro Poroshenko.

Acting on allegations that he sought to overthrow the government, according to a local lawyer, the Ukrainian security service (SBU) detained the politician in Kiev early Tuesday but the police van carrying him was soon surrounded by angry supporters who managed to smash the vehicle's windows and break the former president and ex-governor of Odessa free.

Once released by the crowd, Saakashvili, who founded the Movement of New Forces, addressed his supporters and called for another Maidan revolution to depose Poroshenko and begin the liberation of Ukraine.

The former Odessa governor had on Sunday organized a "March for Impeachment" to demand that parliament adopt laws that allow the president to be impeached, an event that attracted thousands of people.

SBU spokesperson Elena Gitlyanska said the searches were part of criminal proceedings that the Ukrainian prosecutor's office was preparing against Saakashvili.

Saakashvili allegedly had his citizenship revoked by Ukrainian President Petro Poroshenko last July for hiding that he was wanted by Georgian authorities, where he had been president from 2003 to 2012 before that citizenship was also revoked.

Poroshenko's decision was met with a barrage of criticism, as it came shortly after Saakashvili resigned from his role as governor due to rampant corruption in the country's public administration and founded a new political party.