"Naïve" charted at number five on the UK Singles Chart. The best-selling single of the band's career, "Naïve" was also the UK's nineteenth best selling single of 2006. It has also done relatively well in New Zealand, reaching number 15 on the combined sales/airplay RIANZ chart. The song additionally charted in the United States, peaking at number 22 on the Billboard Modern Rock Tracks Chart.
Lily Allen did a cover of "Naïve" for a live session on the Jo Whiley show. Allen's version was featured on the soundtrack for the film Angus, Thongs and Perfect Snogging. The Kooks' original version was featured on the soundtrack for the film 17 Again and on the fourth season, episode "Resolve" of the TV show One Tree Hill as well as on its third soundtrack "The Road Mix".
The song has also been covered by former Sugababes member Mutya Buena as a B-side for her debut single "Real Girl". It placed at #87 in Triple J's Hottest 100 of the Past 20 Years (1993-2013), being one of a few songs to debut in the countdown without having made a yearly list beforehand.