The preparation, characterization, and application in oxidation reactions and antibacterial activity of new biomimetic heterogeneous materials are reported. Brazilian São Simão kaolinite has been functionalized with Fe(III)-[meso-tetrakis(tetracarboxyphenyl)porphinato], [FeTCPP]. Clay functionalization with FeTCPP was confirmed by the amide bands observed in the FTIR spectrum, while UV–vis spectroscopy revealed a red-shift of the characteristic Soret band of the iron porphyrin compared to the parent iron porphyrin in solution, an evidence of FeIII-porphyrin → FeII-porphyrin reduction. Both catalysts reveal complete selectivity for the epoxide in the epoxidation of cis-cyclooctene, while in the Baeyer–Villiger (BV) oxidation of cyclohexanone reached 50% conversion (100% selectivity to ε-caprolactone). The catalysts were recovered and used as antibacterial agents against various bacteria, with activity comparable to that of commercial products such as streptomycin. These results demonstrated that smart multifunctional hybrid organic–inorganic materials that satisfy the demands of Green Chemistry with maximum usability and environmental compatibility can be designed via functionalization of kaolinite.