Cu2O nanocubes were used for the synthesis of hollow and microporous Fe porphyrin networks (H-MFePN). In this synthesis, Cu2O nanocubes performed not only as networking catalysts but also as shape controlling templates. MFePN were formed on the surface of the Cu2O nanocubes through azide-alkyne cycloaddition of tetrakis(4-ethynylphenyl) Fe-porphyrin with 1,4-diazidobenzene. H-MFePN showed excellent catalytic activities in carbene insertion into N-H bonds, maintaining their activities during five recycle tests.