"Masterpiece" peaked at number one in Russia, while reaching the lower regions of the charts in the Czech Republic, Japan, South Korea and the United Kingdom.

[1] Frost was living in Los Angeles at that time and was assessing her priorities in the music world, and wanted to collaborate with a number of artists, Madonna being the first.

[7] In "Masterpiece", Madonna sings about the pain of being in love with someone who is a great work of art, with the lyrics including "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.

"[9] Madonna said the song describes Wallis Simpson and is "about a woman who has fallen in love with this untouchable thing, this man that was raised to be king.

"[5] Marc Schneider from Billboard described "Masterpiece" as a slowed-down, moody ballad that showcases strong execution of vocals from Madonna.

The lyrics were described as emotional, and was comparable to the film's love story, with the chorus as follows: "And I'm right by your side, Like a thief in the night, I stand in front of a masterpiece.

Bradley Stern from MTV wrote that "with its poetic lyrics and gorgeous orchestration, "Masterpiece" is an instant classic addition to Madonna's back catalog of stellar balladry.

"[11] Another review from MTV stated that "the song doesn't follow Madonna's usual style of sexy, energetic and mischievious [sic], rather it shows Madge's wisdom of naked beauty with stripped down vocals, strong penned lyrics and haunting melodies.

[16] Blogcritics editor Tyrone S. Reid called the song a "slow-burning instant classic," which recalls Madonna's Ray of Light era.

[17] A writer for Idolator website said that the song's minimal production "remind[s] us very much of Madge's American Life days, allowing us to focus on the lovely lyrics and Madonna's gorgeous vocals.

[20] Subsequent to the announcement, John's husband, David Furnish, opined on his personal Facebook page that "Madonna winning Best Original Song truly shows how these awards have nothing to do with merit".

[23] "Masterpiece" was also nominated for Best Original Song Written Directly for a Film at the 2012 World Soundtrack Awards, but lost to Albert Nobbs theme "Lay Your Head Down" by Brian Byrne and Glenn Close.

[25][26] The song reached number 25 on the UK Airplay Chart with 26.60 million audience impressions and 660 plays on radio during the eleventh week of 2012.

[27] The song later debuted at number 68 on the UK Singles Chart for issue date of April 7, 2012, due to digital download of the track from MDNA.

[37] The wardrobe during the performance included an all-leather look, a custom design by Hervé Léger and Max Azria, with knee-high boots and a mini fur bolero.

[41] The performance of the song at the November 19–20, 2012, shows in Miami, at the American Airlines Arena were recorded and released in Madonna's fourth live album, MDNA World Tour.

[44] The Atlanta Journal-Constitution's Melissa Ruggieri considered it the show's highlight,[45] while a writer for The Glasgow Herald felt that the performance invigorated Madonna's artistic side.