Acoustica was recorded during three concerts held in February 2001 at the Convento do Beato in Lisbon, Portugal. It was a most unusual set for the band, as Klaus Meine comments on the DVD. The group was supported by female backing vocalists, a percussionist, an extra guitarist, and Christian Kolonovits on keyboards. Kolonovits also collaborated on rearranging the songs for the acoustic set. He had previously worked with the band as a conductor and arranger on the Moment of Glory album.
The Scorpions performed four new songs: "Life Is Too Short", "Back to You", "I Wanted to Cry" and "When Love Kills Love", the last of which was released as a single. All the new songs were featured on the VHS, while "Back to You" and five others were omitted from the CD.
Acoustica also contains cover versions of songs such as The Cars' "Drive", Kansas' "Dust in the Wind", and the Queen hit "Love of My Life".
In 2003, an official 'Platinum Edition' was released by Warner Music Thailand, which coupled the original CD with a VCD. The VCD features behind-the-scenes and rehearsal footage as well as a band interview, conducted in English by a Thai television crew.