A novel type of azobenzene molecule (Azo-diphenylamine) (ADPA) doped in poly (N-vinylcarbazole) (PVK), Poly-butylacrylate (PBA) and 2,4,7-trinitro-9-fluorenone (TNF) was synthesized and studied. The experimental results showed that the polymer film possesses strong photo-induced orientation-enhanced photorefractive effect. The change value of photo-induced refractive index Δn surpasses 1.3×10-3. When irradiated by two-beams, the sample can set up refractive index grating with the diffraction efficiency over 30%. The optical holographic storage was achieved. The factors that influenced refractive index were discussed and the analysis to optical holographic storage was given.