Ponsati, a former Catalan education minister who is now a professor at Scotland's University of St Andrews, is one of the Catalan leaders being sought by the Spanish courts for organizing a referendum on independence in October previous year that was deemed illegal under Spanish law.
She has since resumed working at the University of St Andrews in Fife, but agreed to hand herself in to Scottish police after a European Arrest Warrant was issued.
It is unclear whether the German and Scottish courts will grant the extraditions on the grounds of rebellion.
Ponsati's case, to be heard initially in Edinburgh, may become more legally complex, pitting Scotland, part of the United Kingdom but with its own legal system, against Spain.
"My legal team is instructed to robustly defend Clara as she views these charges as "political persecution" and a systematic attempt to crush the spirit of the Catalan people and their desire for freedom", her lawyer Aamer Anwar said in a statement.
Inigo Mendez de Vigo, a Spanish government spokesman, denied the separatists were "victims", insisting their "criminal actions" were an "attack" not only against Spain but the European Union.
Her solicitor Mr Anwar said on Tuesday: 'I understand that Clara Ponsati faces charges of violent rebellion and misappropriation of public funds which relates to the organising of the referendum, which my client utterly refutes.
It is expected police will place her under arrest and formally serve the European Arrest Warrant on her.
Global arrest warrants are also active against three other politicians who fled overseas past year, and five others are in jail in Spain pending trial.
"She submits that Spain has not followed due process, can not guarantee the independence of the judiciary and has repeatedly abused the human rights of the Catalan people".
Clara Ponsati, Catalonia's former education chief and now a professor at the University of St. Andrews, returned to Scotland in March after fleeing Spain with Puigdemont.
Mr Anwar said Professor Ponsati had been "truly humbled" by the support she had received in Scotland, where many independence supporters have taken a keen interest in events in Catalonia.
"However it is absolutely right that the independence of the judiciary in Scotland is respected and that no government should ever interfere in that process".
On Monday, there were protests outside the Spanish consulate in Edinburgh to demonstrate support for Ms Ponsati.