At the age of twenty, during the de facto government of President Mariano Melgarejo (1864-1871), Villazón founded the newspaper El Ferroviario.

[1] He began his political career at a very young age, joining the Partido Rojo, a party founded by former president José María Linares.

[1][2] At the age of twenty-three, Villazón attended the National Assembly of 1871 which had been called by the government of newly installed President Agustín Morales after the overthrow of Melgarejo.

He was Minister of Foreign Relations during the government of liberal President José Manuel Pando, and he devoted himself to resolving border conflicts with Bolivia's neighboring countries.

He also founded the Oruro School of Mines, today the National Faculty of Engineering, and built railway from Cochabamba to Arani, inaugurated in 1913.

At the end of his term, he handed over the command of his party to his eventual successor, Ismael Montes, who won the general elections of 1913 and was inaugurated as president on August 14.