Catalytic-free coupling of aryl compounds and α-halo cycloketones via in situ generated oxyallyl cation intermediates is reported here. The reactions efficiently afford α-naphthol cycloalkanones with moderate to excellent yields. Electron-rich aromatic compounds are also used to produce the corresponding α-aryl cycloalkanones, and in some cases, analytically pure products are obtained after simple filtration followed by evaporation.