Novel porphyrin with carboxy and its zine and iron complexes were synthesized and characterized by MS, EA, IR, UV-vis and 1H NMR. The fluorescence spectroscopic titration of the iron complex to the zinc complex was used to examine their behavior of supramolecular self-assembly and the results indicated that the fluorescence quenche of the zinc complex was resulted from the formation of zinc complex/iron complex supramolecular by hy- drongen-bonding..