Former Colombian congresswoman Aida Merlano was arrested by Venezuelan security forces on Monday in the northwestern city of Maracaibo after illegally crossing into Venezuela.
Merlano was serving a 15-year prison sentence for vote buying when she staged a spectacular escape in October after giving her guards the slip while visiting a dentist.
"When the competent judge requests the extradition of Mrs Aida Merlano, the national government will make the request before the legitimate government of Venezuela, headed by Juan Guaido," a government statement said.
President Ivan Duque's right-wing government is one of more than 50 countries to recognize Guaido as interim president. Venezuela broke off relations with Bogota in February 2019, after Guaido's failed attempt to breach a border blockade and bring US food and medical aid into the country through Colombia.
Maduro remains in control of all state institutions in Venezuela, with the exception of the opposition-dominated but sidelined National Assembly, which is led by Guaido. The real legislative power in the country lies with the Maduro-controlled Constituent Assembly.
During a visit to a medical center in Bogota to see a dentist on October 1, Merlano managed to slip away from her escorts, climb out a window, and slide down a rope, landing on the sidewalk in front of surprised passersby before calmly escaping on the back of a waiting motorcycle.
A video of her daring escape shot by a nearby security camera went viral on social media.