A Langmuir-Blodgett (LB) inducing method was firstly used to prepare single layer and multilayer conducting composite PEDOT-PSS film. It is shown that better film-processing ability of PEDOT-PSS can be achieved by spreading ODASA mixed monolayer on the PEDOT-PSS sub phase．The Surface of ODA-SA/PEDOT-PSS mixed LB films appears much finer, steady and easy to be controlled with a relatively better ordered structure. Different structures were designed to test the conductive ability of these composite films and a Variable Range Hopping (VRH) model was used to explain the film conductive mechanism. The results indicate that a 3D-VRH model explains well transferring of charge carrier in multilayer film.