The oxidation of sulfides by Oxone((R)) in the presence of catalytic amount of various manganese porphyrins in supercritical CO2 (scCO(2)) has been studied. The reactions have been carried out in an anhydrous two phase-system (solid Oxone((R))) solid catalyst/scCO(2)). In the experimental conditions employed (40 degreesC, 20 MPa), only the new synthesised 5,10,15,20-tetrakis (heptafluoropropyl)porphyrinate manganese(III) chloride showed a slight solubility in scCO(2). In the absence of manganese porphyrin and/or of an aromatic nitrogen base a slow stoichiometric sulfide oxidation leading mainly to sulfoxide is observed ((R)) in scCO(2). Conversely, in the presence of 4-tert-butylpyridine and catalytic in spite of the extremely low solubility of Oxone amount of manganese porphyrins (0.6% with respect to sulfide) enhanced reaction rates are observed. Furthermore, the selectivity of sulfide oxidation reverses and sulfone is formed in larger or comparable amount than sulfoxide even when an excess of sulfide over oxidant is employed. The results collected suggest that the local concentration of the intermediate sulfoxide around the catalyst is higher than that of the bulk supercritical phase thus determining unusual high reaction rates for sulfone formation.