Iron-incorporated ordered carbonaceous frameworks (OCFs) have been synthesized by the pyrolysis of iron porphyrin with ethynyl groups as polymerizable/carbonizable moieties at a temperature higher than 600 °C. The pyrolysis behavior is analyzed by thermogravimetry-differential thermal analysis-mass spectrometry, and the obtained carbon materials are characterized by X-ray diffraction, X-ray absorption fine structure, and high-angle annular dark-field scanning transmission electron microscopy. The introduction of ethynyl groups at the meta positions of the peripheral phenyl groups is essential for efficient cross-linking upon thermal polymerization. The thermally stable polymer thus obtained can be transformed into OCFs with high carbonization yield of 93 % at the subsequent carbonization. OCFs possess periodic structural regularity and porphyrin Fe-N coordination structure, and exhibit electrocatalysis for the conversion of CO into CO. 4 2