A catalyst‐free intermolecular dearomatization reaction of β‐naphthols with hypervalent‐iodine‐based nitrooxylating reagent is reported. Various nitrooxylated β‐naphthalenones bearing a quaternary carbon stereogenic center were obtained smoothly in good to excellent yields (up to 87 %) under mild conditions. This method features mild conditions, broad substrate scope and excellent chemoselectivity.