We present the synthesis and characterization of a hybrid organic–inorganic material using robust metalloporphyrins halogenated in both meso and β-position: the iron complex (5,10,15,20-tetrakis-(pentafluorophenyl) porphyrin and (2,3,7,8,12,13,17,18-octa-β-bromo-5,10,15,20-tetrakis-(pentafluorophenyl) porphyrin, which stabilize the porphyrins against oxidative degradation. The immobilization was developed by the sol–gel process using pyridine and imidazole as template. Electron paramagnetic resonance (EPR) spectra of (2,3,7,8,12,13,17,18-octa-β-bromo-5,10,15,20-tetrakis-(pentafluorophenyl) porphyrin show that the entrapment of ironporphyrin is in a higher symmetry compared to the systems in solution. A reduction of iron was observed in the presence of imidazole, determined by the absence of an EPR spectrum. The addition of chloridric acid vapor induced an oxidation of iron and a small quantity of iron in a high spin state was detected by a component with axial symmetry. The ironporphyrins were active as catalysts for cyclooctene using iodozylbenzene and hydrogen peroxide as oxygen donors. The perhalogenated porphyrins immobilized had a smaller activity due to their iron oxidation and spin states.