A Rh-catalyzed enantioselective dearomatization of 1-aryl-2-naphthols with internal alkynes via C-H functionalization reaction was achieved. In the presence of a chiral Cp/Rh catalyst and combined oxidants of Cu(OAc)(2) and air (oxygen), various highly enantioenriched spirocyclic enones bearing an all-carbon quaternary stereogenic center could be synthesized in 33-98% yields with up to 97:3 er.