It was written by Peter Ries and Charlemaine Thomas-Schmidtner and produced by the former for the band's debut studio album, Elle'ments (2001).

A midtempo pop ballad, "When the Angels Sing" features a cascading piano arrangement and dominant drum pattern.

The music video for "When the Angels Sing" features one of the group's live performances of the song during their Rivers of Joy Tour in fall 2001, intercut by backstage footage of the band.

[1] Ossi Schaller played the guitar, with Ulf Zwerger assisting in its audio engineering, while Dirk Kurock and Trevor Hurst served as Pro Tools editors.

[2] As tracked during the final episodes of Popstars, Ries initially planned to have Nadja Benaissa sing both verses, with Vanessa Petruo leading both bridges.

[2] His plans were not well received within the remaining members of the band who felt that their absence on "When the Angels Sing" ignored their wishes to share lead vocals on all songs and displayed them as backing singers.

[4] It features one of the group's live performances of the song during their Rivers of Joy Tour in fall 2001, intercut by backstage footage of the band.