Initial reports claimed that Madonna had composed the score of W.E. the film with producer William Orbit, and Polish composer Abel Korzeniowski assisting them. However the latter was credited as the sole music composer for the film. Madonna had heard Korzeniowski's work on the soundtrack for the 2009 drama film, A Single Man.

The singer recalled that she was "struck by the score's 'bittersweet' qualities, this melancholic, romantic, sweeping emotional kind of heartbreaking beauty."She asked the film's director, fashion photographer Tom Ford, about Korzeniowski and after she received positive feedback about him, she decided to sign Korzeniowski for composing W.E.'s score.

Previously, Madonna had included parts of the score from A Single Man into the rough cut for W.E., as well as in some of the screenplay. The score predominantly features usage of strings, accompanied by electric guitar, harp, viola and piano. The combination of traditional and modern instrumentation was used to bridge the two different time-periods portrayed in the film.

Korzeniowski recorded a 60-piece orchestra at London's Abbey Road Studios, concentrating on purely the emotional states of the characters, and did not concern himself too much with differentiating the periods of the film. In an interview with Variety, the composer said that for the scenes featuring Simpson, he tried to make the score be more modern than the scenes featuring Winthrop.

Madonna wanted Korzeniowski to keep the score simple and direct. She felt that Korzeniowski being a classically trained musician, he would be cerebral in his approach to music and would over complicate the score. "It is not the type of score where you go through crazy harmonic changes and modulations," said the composer. "This was one of the very precise notes I got from Madonna, that I was not supposed to over-think this music."

Madonna contributed a new song titled "Masterpiece" for the soundtrack, composed by herself, Julie Frost and Jimmy Harry, while produced by Orbit. In the song, she sings about the pain of being in love with someone who is a great work of art, with the lyrics going like "If you were the Mona Lisa, You'd be hanging in the Louvre, Everyone would come to see you, You'd be impossible to move." A writer from Billboard described "Masterpiece" as a slowed-down, moody ballad that showcases strong execution of vocals from Madonna. He described the production as "simple, direct and reminiscent of her sound in the 1990s".

The lyrics were described as emotional, and was comparable to the film's love story, with the chorus going on like: "And I'm right by your side, Like a thief in the night, I stand in front of a masterpiece. And I can't tell you why it hurts so much to be in love with a masterpiece." The song will play over the end credits of W.E. and would be included in Madonna's upcoming album, M.D.N.A.

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