A Langmuir-Blodgett (LB) inducing method was firstly used to prepare single layer and multilayer conducting composite PEDOT-PSS film. The film-forming ability of ionization ODA and ODA-SA monolayer spread on PEDOT-PSS nanoparticle sub-phase and the behavior of ODA/PEDOT-PSS assembly particles on pure water were fn-stly investigated. The results indicated that nanopartieles in the suphase are packed in the ionization monolayer and stable complex Langmuir film is formed at the air/water interface. It has been found that the best film-forming conditions for composite film are as follows: distinct interface was formed between ODA and PEDOT-PSS layer and single layer thickness of PEDOT-PSS was about 23 nm, well accordant to the size of PEDOT-PSS nanoparticles. 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 indicated that a 3D-VRH model explained well the transferring of charge carder in the multilayer film.