Following her success as a child star, Dulce began to start in teen-oriented telenovelas such as El Juego de la Vida and Clase 406. In Clase 406, she worked alongside Alfonso Herrera, Anahí, and Christian Chávez, who later became her bandmates in RBD. In 2004, she was cast as one of the main characters in Rebelde, a Mexican remake of the hit Argentinian soap opera, Rebelde Way. Dulce played Roberta Pardo, the strong-willed daughter of a famous Mexican singer. Rebelde was a hit worldwide and had over 400 episodes, lasting from 2004 and 2006. In 2006, the actress received the award TV Y Novelas, as Best Young Telenovela Actress for Rebelde.

Following the success of Rebelde, in 2007, Televisa released RBD: La Familia, which starred the members of RBD. The series was based on the fictional lives of 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 November 25, 2008, Dulce collaborated with Tiziano Ferro and Anahí on a song called El regalo más grande.

In 2009, after the split up of RBD, she starred in the telenovela Verano de Amor, along with Gonzalo Garcia Vivanco and Ari Borovoy, also produced by Pedro Damián, where she interprets the theme songs of the telenovela, Verano (Summer) and Déjame Ser (Let Me Be). Dulce was cast as Miranda. The novela premiered on February 9, 2009, replacing the ended series Juro Que Te Amo. Verano de Amor incorporates messages into the novela promoting environmental responsibility, an extension of Televisa's Televisa Verde initiative focused on the environment.

In 2010 she received the prize, People En Español as Best Young Actress on the soap opera Verano de Amor. On April 2010, Dulce María started a new project in a film, directed by Gonzalo Justiniano Alguien Ha Visto A Lupita? (Has Anyone Seen Lupita?) starring alongside actor Chilean Cristian de la Fuente. The film aims to be released in March 2011 and be presented at film festivals at an international level. Following the breakup of RBD, Dulce announced that she will begin recording in 2009 as a solo artist. Her first solo single released on May 17th 2010 is Inevitable, the music video was released on May 24, showing Dulce taping a guy to a chair then singing to him, in an abandonded ware house. The video was directed by Argentinean director Francisco d'Amorim Lima. The song is still charting in many countries, such as Mexico, Spain, Slovenia, United States and Argentina. Her first solo album Extranjera is set to debut in september 2010.