The Cu(II)-catalyzed oxidative and reductive cleavage of the disulfide bond of N-(2-(2-(2-picolinamido)phenyl)disulfanyl)phenyl)picolinamide, L, is reported for the first time. Aerobic oxidation with Cu(II) gives complete oxidation of S-S bond to sulfonates, whereas Ag(I) gives only partial oxidation up to sulfinates, in the absence of any other oxidizing agent, in tetrahydrofuran/water solution. The in situ generated sulfonate product forms a thermally stable, two-dimensional H-bonded polymeric complex with Cu(II) ions in two polymorphic forms. L in the presence of Cu(II), in an inert atmosphere, results in a reductive cleavage of the disulfide bond and an in situ formation of a new C-S bond. The latter forms a unique tetranuclear complex with Cu(II) employing deprotonated amide groups and bridging thiol and chloride atoms. The disulfide precursor and the products were characterized by X-ray crystallography and spectroscopic techniques.