A heterogenized Mn(III) porphyrin-based catalyst was prepared for dye degradation. The new Mn(III) complex of 5,15-bis(4-aminophenyl)-10,20-diphenylporphyrin was immobilized, via covalent bond, in chloropropyl silica gel, generating the material (Sil-Cl@MnP) with a loading of 23 μmol manganese porphyrin (MnP) per gram of Sil-Cl. This material was used as a catalyst in degradation reactions of model dyes, a cationic dye [methylene blue (MB)] and an anionic dye (reactive red 120, RR120), using PhI(OAc) 2 and H 2 O 2 as oxidants. The oxidation reactions were carried out after the dye reached adsorption/ desorption equilibrium with the catalytic material, with a much higher percentage of adsorption being observed for the cationic MB dye (20%) than for the anionic RR120 dye (3%), which may be associated with electrostatic attraction or repulsion effects, respectively, with the negatively charged surface of the silica (zeta potential measurement for Sil-Cl@MnP, ζ = −19.2 mV). In general, there was a higher degradation percentage for MB than for RR120, probably because the size and charge of RR120 would hinder its approach to the MnP active species on the silica surface. With respect to the oxidant, the PhI(OAc) 2 -based systems showed a higher degradation percentage than those of H 2 O 2 . It was observed that the increase in the oxidant concentration promoted a significant increase in the degradation of MB, with a degradation of approximately 65%. The efficiency of the catalyst was also evaluated after successive additions of the oxidant every 2 h, and it can be seen that the catalyst had no loss of efficiency, with a degradation percentage greater than 80% being observed after 8 h of reaction. The phytotoxicity of the products formed in the system was evaluated in a 1:23.5:188 molar ratio Sil-Cl@MnP: MB:PhI(OAc) 2 was used. In these studies, phytotoxicity was found for the germination of lettuce seeds when the original solution was used without dilution; however, when diluted (10% V/V), the results were close to the positive and negative controls. Thus, the material obtained proved to be a potential candidate for application in the degradation reactions of environmental pollutants.