© 2020 American Chemical Society. A chemoselective dearomatization of the less reactive benzenoid unit in β-naphthol was developed. Spirocyclization with a reductant constructs a pivotal structure for drug candidates. One-pot oxidative conversion enabled the tandem dearomatization of β-naphthol, producing conjugated tetraenone variants. The potential utility of the product as an F-selective anion sensor was also demonstrated. Theoretical studies revealed the intermediacy of silver-carbenoid species leading to chemoselective spirocyclization over arene cyclopropanation.