This Spanish language tune features the Dominican singer Juan Luis Guerra. Iglesias had Guerra in mind for this song for a long time. The Latin superstar Guerra is an idol of Iglesias, but someone he barely knew, and he was concerned that he wouldn't be interested in the collaboration as Guerra only records his own songs. "I didn't think he was going to say 'yes.' And he didn't," Iglesias recalled to Billboard magazine. "He said, 'I really can't give you an answer unless I hear the song.'" To Iglesias' surprise, Guerra not only accepted, but also agreed to participate in the song's music video.
Released as a single, the song proved to be a big hit, topping Billboard Hot Latin Songs and also the Mexican singles chart.
The song was used as the main-theme for the Mexican soap opera also titled Cuando Me Enamoron, starring Silvia Navarro and Juan Soler.
The music video was filmed in a college on San Patricio in Jersey City, New Jersey. Iglesias and Guerra play guest stars singing at a school and the clip also features Ugly Betty actress Ana Ortiz as the college director.