Some thermal stable fluorine-containing polymides with side-chain second-order nonlinear optical (NLO) chromophores have been developed, which were prepared by one primidized, hydroxyl polyimide, follwed by the covalent bonding of a chromphore onto the weight percent. Dteailed physical properties showed that the resulting polyimides have good solubility in common organic solvents, relative high glss transition temperatures. Polymer waveguide devices can be easily spin-coated, ensuring a long-term alignment stability at elevated temperatures. These devices exhibit large electro-optic coefficients, 25pm V-1 at 0.83μm, which reained>95% at 120℃ for more than 100h.