Her second and third studio albums, Un mondo perfetto and Il popolo dei sogni, were released in 2005 and 2006, and they were both awarded platinum for sales in Italy.

In 2006, a compilation album including tracks from these two records, titled Un mondo perfetto, was released in Germany, Switzerland and Austria only.

Her first studio album for a major label, Dolcenera nel paese delle meraviglie, was released for Sony Music in 2009 and spawned the hit single "Il mio amore unico".

Dolcenera was also a member of the supergroup Artisti Uniti per l'Abruzzo, which released the charity single "Domani 21/04.09", and she appeared as a featured artist on the Italian version of British rapper Professor Green's single "Read All About (Tutto quello che devi sapere)", included both in his album At Your Inconvenience and in Dolcenera's Evoluzione della specie².

During her career Dolcenera appeared on the albums of other Italian recording artists, including Roberto Vecchioni, Claudio Baglioni and the progressive rock band Premiata Forneria Marconi.