President Rafael Correa noticed that Calle spoke in support of the government's idea of a Constituent Assembly when she visited the Palacio de Carondelet.

When the Constituent Assembly was installed in December 2007, she was appointed president of the Latin American Sovereignty and Integration table with Gabriela Quezada as her deputy.

She said that in revenge for this she was accused of allowing her bank account to be used by the FARC leader Raúl Reyes in 2006.

She attracted attention during her second term when she championed the idea that "media lynching" should be added to the Penal Code.

[3] In 2017 she was appointed Ecuador's ambassador to Cuba by President Lenín Moreno, becoming the first woman to hold that position.