A novel [4 + 1] and [5 + 1] dearomative spiroannulation has been developed by the use of commercial naphthols and phenols with dielectrophiles. Various spirocycles, including spiro[4.5] and spiro[5.5] have been constructed successfully by employing four-atom or five-atom dielectrophilic synthons. This transformation was realized through a sequence of site-selective C-alkylation/dearomative spiroannulation. Moreover, the potential application of this method was exemplified by several further transformation.