The show stars Anahí, Dulce María, Alfonso Herrera, and Christopher von Uckermann, with Maite Perroni in her debut role, and Christian Chávez.

It features Juan Ferrara and the stellar performance of Ninel Conde as the adult protagonists, with Enrique Rocha and Tony Dalton as the antagonists.

Due to its school setting, it contains an ensemble cast, including Angelique Boyer, Estefanía Villarreal, Karla Cossío, Zoraida Gómez, Jack Duarte, and Eddy Vilard.

Another notable aspect is that the actors playing the band members are themselves in an actual group named RBD and perform most of the music used on the telenovela, including the opening theme song, "Rebelde".

The group achieved international success from 2004 until their separation in 2009 and sold over 15 million records worldwide, making them one of the best-selling Latin music acts of all time.

Among the students are Mía Colucci Cáceres (Anahí), Roberta Pardo Rey (Dulce María), Miguel Arango Cervera (Alfonso Herrera), Diego Bustamante (Christopher von Uckermann), Guadalupe "Lupita" Fernández (Maite Perroni) and Giovanni Méndez López (Christian Chávez).

Girls also wear regulation underwear: full-cut black briefs with matching sport-bras, as demonstrated by Mia in the series' pilot.