A novel azobenzene optically polymer (P-DA) was synthesized based on the azo chromophore molecule, chiral reagent L(-)-tartaric acid, acryloyl chloride and methacrylate. The P-DA was characterized by FT-IR, UV-Vis spectroscopy, 1H NMR, DSC and TGA. The P-DA had high thermal stability up to its glass-transition temperature (Tg) of 110 oC and 5 % heat weight loss temperature of 199 oC. The UV-induced trans/cis photoisomerization and reflex-isomerization behaviors were investigated. The results indicated that the P-DA solution could undergo photochromism after irradiated by 365 nm UV light. The optical parameters: refractive index (n), the dielectric constant (ε) and thermal volume expansion coefficient (β) of P-DA were obtained. The thermo-optic coefficients are one order of magnitude larger than those of the inorganic materials, such as SiO2 (1.1×10−5 oC -1 and LiNbO3 (4×10−5 oC -1) and was larger than the organic material such as polystyrene (-1.23×10-4 oC -1) and PMMA (-1.20×10-4 oC -1). The conclusion had a little significance to develop optical communication.