The fluorine-containing organic polymer was synthesized from 3, 3＇, 4, 4＇-Bisphenyltetracarboxylic （BPDA）, and 2,2-Bis （3-amino-4-hydroxyyphenyl） hexafluoropropane （6FHP）. It is a first-step preparation of a preimided hydroxy-containing polyimide, followed by the covalent bonding of an active chromophore, dispersed red 19 （DR19）, onto the backbone of the polyimide via the Mitsunobu reaction. The nonlinear optical （NLO） containing polyimide was synthesized. The differential scanning calorimeter （DSC）and thermal gravimetric analysis （TGA） exhibited Tg and the temperature Tg at which 5 % mass losses occurring of polymer were 248 and 309 ℃, respectively. A reflective electro-optic （EO） modulator using this polymer was fabricated. The optical nonlinearities were determined to be d33 = 5. 209×10^-9 esu （poling voltage of 3.6 kV, 205 ℃） and d33 =7. 418×10^-9esu （poling voltage of 3. 8 kV, 210 ℃） by the second harmonic generation method in in-situ condition at a fundamental wavelength of 1 064 nm. The EO coefficients 733 of the polymer layer in the EO modulator were determined to be 2. 182 pm/V （poling voltage of 3.6 kV, 205 ℃） and 3. 107 pm/V （poling voltage of 3.8 kV, 210 ℃） at 1064 nm by an attenuated-total-reflection （ATR） method.
