We developed new composite polymer system with monolithic azo dye substances (NACzE and NACzH) and high optical quality polymer hosts (PMMA and PEMA), and obtained quite high photorefractive performances of two beam coupling (2BC) gain 451 cm(-1) (PMMA/NACzE) and 340 cm(-1) (PEMA/NACzH), respectively, without applying external electric field.