We report the electro-optical (E/O) characteristics of the Langmuir-Blodgett film of poly(vinylidene fluoride with trifluoroethylene) copolymers. The structural origin of E/O response of nano LB films was discussed with the result of temperature dependent E/O response at a temperature range from 20 to 100 degrees C. Thermal hysteresis of E/O response and the ferroelectric-paraelectric phase transition were observed at a 20 monomolecular layers Langmuir-Blodgett films.