In addition to the Isley Brothers sample, the song features use of keyboards, synthesizers, and electric guitars. "Luxurious" is an R&B ballad whose lyrics describe the persona's desire to be rich in love, simultaneously comparing her lover with luxuries. The song also features Stefani's husband Gavin Rossdale who opens the song in French.
The song was released as the album's fifth single in October 2005 along with a remix featuring rapper Slim Thug. A music video was also released which featured Slim Thug, as well as the Harajuku Girls. The track received mixed reviews from critics, who generally found it less impressive than the previous singles. It charted within the top 40 in several countries, but had mediocre success overall and was less popular than the previous singles from Love. Angel. Music. Baby.