New microporous polymer networks, constructed by a nucleophilic substitution reaction between two different porphyrins and metalloporphyrins are reported. The meso-tetrakis-(pentafluorophenyl)por phyrin HP1 (monomer A1) and/or its manganese complex MP1 (monomer A2) was reacted with the meso-tetrakis-(3,4-dihydroxyphenyl)porphyrin HP2 (monomer B1) and/or its manganese complex MP2 (monomer B2), giving rise to four new porphyrin-based microporous network polymers (P1-P4) with apparent BET surface areas in the range 600-1200 m(2) g(-1). The catalytic performance of the polymers was evaluated by oxidation reactions using cyclooctene and cyclohexane as substrates and lodosylbenzene as oxidant in cytochrome P-450 model reactions. The catalytic activity and selectivity of these porous polymer networks are similar or superior to those of the analogous homogeneous manganese porphyrins MP1 and MP2. The robustness of the materials in terms of thermal stability and good recyclability showed that they hold great promise as biomimetic heterogeneous catalysts. (C) 2018 Elsevier Inc. All rights reserved.