In 1867 and then again in 1889, Rodríguez de Tió and her husband were banished from Puerto Rico by the Spanish Governors. On their first exile they went to Venezuela and on their second banishment they first moved to New York where she helped José Martí and other Cuban revolutionaries and later to Cuba where the couple resided until their respective deaths. Their home became a gathering point for politicians and intellectuals as well as exiled Puerto Ricans. In 1868, inspired by Ramón Emeterio Betances's quest for Puerto Rico's independence and by the attempted revolution called the Grito de Lares, she wrote the lyrics to the existing tune of La Borinqueña. In 1901, Rodríguez de Tió founded and was elected member to the Cuban Academy of Arts and Letters. She was well known in Cuba for her patriotic poetry about Puerto Rico and Cuba.