The metal-catalyzed autooxidation of S(IV) has been studied for more than a century without a consensus being obtained as to reaction rates, rate laws or mechanisms. The main objective in this work was to explore the reaction between Cu(II) and SO2 in the presence of M(II), paying special attention to the formation of double sulfites like Cu2SO3.M(II)SO3.2H 2O. The two principal aspects studied were: i) a new way to prepare double sulfites with high purity degree and the selectivity in the M(II) incorporation during the salt formation.