Coordination bonding driving supramolecular self-assembly of Zn(TPP) with Fe(p-ImEPTPP)Cl was investigated by fluorescence spectra and 1H NMR. The results indicate that an obvious fluorescence quenching observed from Zn(TPP) by addition of Fe (p-ImEPTPP)Cl is due to the coordination of the terminal imidazolyl group of Fe(p-ImEQTPP)Cl to Zn2+ of Zn(TPP). The change of fluorescence spectra of Zn(TPP)/Fe(p-ImEPTPP)Cl system by adding some Lewis bases, such as piperidine, imidazole and pyridine, as well as 1H NMR further supported this coordination.