Three new porphyrin derivatives were synthesized from tetra (4-aminophenyl) porphyrin (TAPP), namely tetra[p-(4-cyanophenylmethylene imino)]phenyl porphyrin (TCyPPP), tetra[p-(P-benzylidene)]phenyl porphyrin (TbePPP) and tetra[p-(4-pyridylimethylene imino)]phenyl porphyrin (TPyPPP). Based on the principle of self-assembly, three kinds of porphyrin derivatives were self-assembled to prepare three kinds of monomers. The structures were characterized clearly by UV-vis, FT-IR, ¹H NMR and SEM. The photocatalytic performance study shows that the self-assemblies of the three porphyrin derivatives have stronger photocatalytic performance than their monomers. Moreover, the self-assemblies and their monomers have good photocatalytic stability.