Synergistic catalysis occurring in an enzyme pocket shows enhanced performance through supramolecular recognition and flexibility. This study presents an aerogel capable of similar function by fabricating a gel catalyst with hierarchical porosity. Here, the as-prepared Co-MMPG, a Co(II) metal-metalloporphyrin gel, maintains enough conformational flexibility and features a binding pocket formed from the co-facial arrangement of the porphyrin rings, as elucidated through the combined studies of solid-state NMR and X-ray absorption near-edge structure (XANES). The cooperativity between two Co(II) sites within the defined nanospace pocket facilitates the binding of different substrates with a favourable geometry thereby rendering Co-MMPG with excellent performance in the context of synergistic catalysis, especially for the kinetic control stereoselective reactions. Our work thus contributes a different enzyme-mimic design strategy to develop a highly efficient heterogeneous catalyst with high chemo/stereo selectivity.