Both of dianhydride and diamines are made to synthesize second-order nonlinear optical polyimides containing side-chained benzobisthiazole based chromophores by method of chemical cycle. Then, this study regarded high Tg and high thermal stability of polyimides as main-chain of polymers and this study regarded high dipolemoment of chromophores as side-chain of polymers Finally, combine two parts into two kind of nonlinear optical polyimides. By changing the structure of main-chain and side-chain, chromophore poled can reduce space-hinder and enhance the electrooptical coefficient r33. This study can identify functional group, the larger absorption wavelength and dissocation temperature of structure of nonlinear optical polyimides by instruments of IR, UV, TGA,¡Ketc. In the measurement of nonlinear optics, polymers owning both of larger dipoleminents and -ether group are regularly poled in characterisitc orientation. Therefore, these polymers have a higher electrooptical coefficient r33. In this results, the r33 of NLO-PIB film is 7.70 pm/V and the r33 of NLO-PIB film is 7.64 pm/V at room temperature.