A new intercalation compound of layered perovskite (K4Nb6O17 center dot 3H(2)O) with cationic Co-porphyrin 5,10,15,20-tetrakis(N-methylpyridinium-4-yl) porphyrinato cobalt(III). CoTMPyP, was successfully synthesized by a guest-exchange method using PrNH3+-Nb6O17 as an intermediate. The resulting nanocomposite CoTMPyP-Nb6O17 has been characterized by X-ray diffraction, elemental analysis, scanning electron microscopy and UV-vis absorption spectra. The glassy carbon (GC) electrode modified with CoTMPyP-Nb6O17 film exhibited two well-defined redox waves at -0.77 and -0.56V, corresponding to the (CoTMPyP)-T-II/I and (CoTMPyP)-T-III/II couple (vs. SCE. in pH 12.0 phosphate buffer solution). The catalytic performance of the novel catalyst CoTMPyP-Nb6O17 for the epoxidation of cyclohexene was investigated using molecular oxygen as oxidant and isobutylaldehyde as co-reductant. The intercalated cobalt porphyrin appears to be a promising catalyst owing to its good catalytic activity and selectivity. CoTMPyP-Nb6O17 could be reused and showed no appreciable decrease in activity after six reaction cycles. (C) 2012 Elsevier B.V. All rights reserved.