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 nanoparticles subphase and the behavior of ODA/PEDOT-PSS assembly particles on pure water were firstly investigated. The results indicate that nanoparaticles in suphase pack the ionization monolayer and stable complex Langmuir film was formed at air/water interface. It has been found that the best film-forming conditions for composite film were as follows: molar ration of ODA to SA was 2:1, suphase temperature was 23 centigrade, concentration of PEDOT-PSS in subphse was about 1×10-3 M, and compressing speed and deposition speed were 5 mm/min and 1 mm/min respectively. The SIMS and XRR investigation show that this film exhibits well ordered layer structure.