A full IR, UV-Vis, FIR, spectroscopic analysis on substituted porphyrin iron, manganese, cobalt, copper and Zinc complexes was performed, and the spectroscopic patterns were found for the metalloporphyrin compounds with various structures. Base on molecular structures theory, the reasons for the spectroscopic patterns were discussed deeply. Considering the inconsistency of the far-infrared spectra of the Fe-Cl axial bonds in chloro-iron tetraphenylporphyrins reported in the literature. Their far-infrared absorptions were investigated by using both theoretical analysis and experimental determination, and the results showing that their vibrational frequencies of the Fe--Cl bonds in different substitution chloro-iron tetraphenylporphyrins were associated with their structures, and were linearly related to the length of Fe--Cl bonds.