Following his completion at the Centro de Educación Artística, Herrera began working professionally in theater. He performed in "Las Brujas de Salem," "Como matar a un ruiseñor" and "Antigona." In 2002, he was cast in the film "Amar te duele," directed by Fernando Sariñana, and from there moved into television, working in the telenovela "Clase 406," alongside Dulce Maria, Anahí, and Christian Chávez, who later became his bandmates in RBD.

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.

In 2007, Herrera began filming "Volverte a Ver" with Ximena Herrera. It was released in December 2008. The movie was filmed in Mexico and Argentina. In 2008, he also starred in the play "The Pillowman," replacing actor Kuno Becker.

In 2009, he began filming "Venezzia in Venezuela," alongside Ruddy Rodríguez. 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.

In 2009, he also guest starred on an episode of "Mujeres Assesinas," Soledad, Cautiva, alongside his 'Rebelde' co-star, Angelique Boyer. 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 involved in a television series called "El Diez" where he plays a soccer player named 'Chava Espinoza'. This series airs on ESPN Deportes; which is available in the United States as well as some Latin American countries.

On August 19, 2011, Herrera's most recent movie 'Así es la Suerte' premiered. In 2015, he was portrayed as the role of Hernando in the Netflix series "Sense8."