Effect of different reaction parameters on the catalytic activity of β-tetrabrominated meso-tetra(para-tolyl)porphyrinatomanganese(III), MnT(4-CH3P)PBr4(OAc) , for oxidation of different sulfides and hydrocarbons with tetra-n-butylammonium hydrogen monopersulfate (TBAHS) has been studied. In oxidation of sulfides, the chemoselectivity of reaction has been significantly changed in THF as the solvent compared with the common organic solvents. Also, using nitrogenous bases bearing electron-withdrawing groups ( -Cl or -CN ) clearly increased the ratio of sulfoxide to sulfone relative to the electron-donating ones. Catalytic oxidation of olefins with TBAHS was conducted in protic and aprotic solvents and acetonitrile has been found as the best solvent. A significantly large difference was found between the co-catalytic activity of imidazole (ImH) and pyridine in comparison with that observed in dichloromethane. The competitive oxidation of cis- and trans-stilbene suggests the presence of a high valent manganese oxo as well as a six coordinate (ImH)MnT(4-CH3P)PBr4(HSO5) species as the active oxidants in acetonitrile.