In this paper properties of P(VDF/TrFE) polymeric planar waveguides were studied by prism couple method and polarized light reflect technique.The uniform and transparent polymeric planar waveguides were obtained when the concentrations of P(VDF/TrFE) solution were properly made up and the polarization temperature was something raised.The influences of crystalline grains and crystalline boundaries inside the P(VDF/TrFE) polymer films obtained on the optical properties were improved.The samples were prepared by spin coating method.The conditions of prepared processes on the optical properties were discussed.