The construction of bilayer or multilayer structures has been recognized as one of the most promising strategies for exploring high-performance organic thermoelectric materials. In this study, a novel poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate)/polyaniline (PEDOT:PSS/PANI) bilayer film was successfully fabricated through a facile solution method, wherein PANI was initially dissolved in concentrated sulfuric acid (H2SO4) to form a homogenous solution which was then applied to the PEDOT:PSS film. Benefiting from the introduction of PANI, the Seebeck coefficient of the PEDOT:PSS film was improved from 16.34 to 23.17 μV K−1, while the electrical conductivity experienced a remarkable enhancement, reaching 723.34 S cm−1. Accordingly, the resulting PEDOT:PSS/PANI-H2SO4 bilayer film demonstrated a high power factor (PF) of 38.83 μW m−1 K−2, which further increased to 44.38 μW m−1 K−2 at 380 K. Hence, this technique offers a facile method to fabricate large-scale PEDOT:PSS/PANI-H2SO4 bilayer films, expanding application fields of PANI via solution-based preparation.