Following his completion at the Centro de Educación Artística, Herrera began working professionally in theater. He performed in Las Brujas de Salem (2001), Como matar a un ruiseñor (2001) and Antigona (2001).
In 2004, he was cast as one of the main characters in Rebelde, a Mexican remake of the hit Argentine novela, Rebelde Way. Herrera played Miguel Arango, a teenager who moves to Mexico City to avenge his father's death. Rebelde was a hit worldwide and had over 400 episodes, lasting from 2004-2006.
Following the success of Rebelde, in 2007, Televisa released RBD: La Familia, which starred the members of RBD. The characters of the sitcom were not based on the band's characters in Rebelde, but intended to be similar to the actors' real personalities. RBD: La Familia was the first Mexican show shot entirely in High Definition. The show ran from March 14, 2007 – June 13, 2007, and only lasted 13 episodes.
On May 21, 2009 it was announced that Herrera would star alongside Spanish Mexican singer/actress Belinda Peregrín in Televisa's latest novela, Camaleones. Herrera played Sebastián, a man who pretends to be a professor and steals expensive art work in order to protect his jailed father.
Herrera also worked alongside actors Plutaco Haza, Paola Núñez, Sergio Klainer, Guillermo Larrea, Jana Raluy, and Raúl Vallejo on the Spanish version of Rain Man, known in Spanish as Cuando los hermanos se encuentran.
Besides Rain Man, 2011 has brought up new projects for Herrera. He worked on a television series called El Equipo (The Team) produced by Pedro Torres where he played a federal policeman named Fermín Pérez. This series has been compared to the television series CSI and was aired in Mexico as well as the United States.
Alfonso is currently filming a television series called "El Diez" where he will play a soccer player named 'Chava Espinoza'. This series will be aired soon on ESPN Deportes; which is available on the United States as well as some Latin American countries.
On August 19, 2011, Herrera's most recent movie 'Así es la Suerte' will premier on theaters around various areas in Mexico. He will star in Salvador Mejía's new telenovela: La tempestad.
The success of Rebelde, launched RBD. To date RBD has made 9 studio albums, including albums in Spanish, Portuguese and English. They have sold over 15 million albums worldwide, and have toured across Mexico, South America, Serbia, Romania, the United States and Spain.