The orthometalated [1-(dimethylamino)ethyl]naphthalene platinum(II) complex has been used successfully to promote the asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylphosphole and sulfoxide in high selectivity. The exo-cycloadduct coordinated to the platinum template as bidentate chelates via their phosphorus and sulfur atoms. The dichloro platinum complexes could be crystallized and were stable in the solid state as well as in solution. Optically pure P鈥揝 bidentate ligands could be liberated from these dichloro complexes by treatment with aqueous potassium cyanide. The study also highlights the difference in reactivity and mode of substrate activation between an earlier study involving a Pd analogue of the template and the current results.