New hybrid organic–inorganic materials are prepared by hydrolysis and polycondensation, or cocondensation with tetraethyoxysilane, of iron porphyrins bearing a trifluorosily function; despite their insolubility, these ‘metalloporphyrinosilicas’ are efficient catalysts for alkene epoxidation by PhiO or Bu^tOOh and alkane hydroyxylation byPhIo, the iron porphyrinosilics with low specific surface areas (≈ 60 m² g^–1) catalysing a shape-selective hydroxylation of alkane mixtures.