The track is a heavily-synthesized ballad in which Lennox takes the role of a suspicious girlfriend demanding to know who the various women are with whom she has seen her lover associating. The song became Eurythmics' third Top 10 single in the UK singles chart, peaking at number three. In the United States, "Who's That Girl?" was released as the follow-up to the Top 10 "Here Comes the Rain Again" and it climbed to number twenty-one on the Billboard Hot 100.
The music video became a heavily-played clip on MTV and further showcased Lennox's gender-bending image. In it she appears as a nightclub singer performing the song (complete with 1960's-era blonde flip wig) and also as a man who is a member of the audience. Stewart appears in the video, flirting and carousing with various women. Although they became romantically linked years later, Stewart's future wife, Siobhan Fahey, appears as one of the women and the other two members of Bananarama also make cameo appearances.
Other "girls" include Cheryl Baker and Jay Aston of Bucks Fizz, Kiki Dee, Hazel O'Connor, Kate Garner of Haysi Fantayzee, Thereza Bazar of Dollar and Marilyn. Ironically Jacquie O'Sullivan appears in the video — she would, four years later, become Fahey's replacement as a member of Bananarama.
In the end of the clip, the female-Lennox is shown kissing the male-Lennox.
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