Novel polymers containing zinc porphyrins are synthesized from 5-(4-acryloyloxyphenyl)-10,15,20-trisphenylporphyrinate zinc(II) (ZnAOTPP) and NVP. The polymer microspheres are obtained by polymerization in alcoholic solution. TEM images and particle size distribution data show that the morphology and size of the polymer microspheres are controlled by adjusting the molar ratio of ZnAOTPP (RM) to solvent in the polymerization. Compared with ZnAOTPP, zinc porphyrin units (ZnPor units) in polymers exhibit a new absorption band and a new fluorescence emission band due to the formation of porphyrin assemblies, which improve the color purity of their red fluorescence. The luminescence of the polymer microspheres is characterized by fluorescence microscopy.