This paper describes the synthesis and physical study of several new photorefractive polymers. The Heck reaction was successfully applied in the synthesis of these multifunctional polymers. These polymers are conjugated poly(phenylenevinylene)s copolymerized with a small amount of macrocyclic zinc complexes as the photosensitizers. Nonlinear optical chromophores were incorporated as the pendant groups. Both electron-rich and electron-deficient PPV backbones were synthesized. Experimental results showed that when an electron-rich photosensitizer is used, the electron-deficient component for charge transport (CN-PPV) enhances photorefractive performance and reduces the response time.