A new approach for the fabrication of organic-organic conducting composite thin films using simultaneous co-vaporization vapor phase polymerization (SC-VPP) of two or more monomers that have different polymerization mechanisms (i.e., oxidation- coupling polymerization and radical polymerization) was reported for the first time. In this study, a PEDOT-PSMA composite thin film consisting of poly(3,4-ethylenedioxythiophene)(PEDOT) and poly(styrene-co-maleic anhydride)(PSMA) was prepared by SC-VPP process. The preparation of organic-organic conductive composite thin films was confirmed through FT-IR and 1H-NMR analyses. The surface morphology analysis showed that the surface of PEDOT-PSMA thin film was rougher than that of PEDOT thin film. Therefore, PEDOT-PSMA exhibited lower electrical conductivity than that of PEDOT. But the conductivity can be improved by adding 2-ethyl-4-methyl imidazole as a weak base. The contact angle of PEDOT-PSMA was about 50°, as compared to 62° for PEDOT. The demonstrated methodology for preparing an organic-organic conductive hybrid thin film is expected to be useful for adjusting intrinsic conductive polymer (ICP)’s surface properties such as mechanical, optical, and roughness properties.