 "Call the Shots" received positive reviews from music critics. Alex Fletcher of Digital Spy rated the song four out of five stars, writing that it is "more tasteful" than few of Girls Aloud's previous releases. Daily Star journalist Kim Dawson said "Call the Shots" is one of the band's best singles, while another reviewer for the same newspaper deemed the song "classy electronic Euro-pop with real edge." Jennie McNulty of Marie Claire said that the song "has a wonderfully ambient feel, echoing an arty electro band", while Alexis Petridis of The Guardian wrote that Tangled Up "begins disappointingly" with "Call the Shots" as the opening track because the song's structure is "a bit commonplace" compared to Girls Aloud's previous singles such as "Biology" (2005). On the countdown of the top singles of 2007, Digital Spy placed "Call the Shots" at number 17, commenting that the band had not lost "their knack for making supremely catchy pop hits." In 2008, the song won the Popjustice £ 20 Music Prize – Girls Aloud's fourth win. Popjustice writer Peter Robinson deemed it as the "greatest pop song of the 21st century."
