Polyaniline (PANI) composite films were prepared on silicon and quartz glass substrates by electron beam deposition (EBD), using polyvinyl chloride (PVC), aluminum trichloride (AlCl3), and mixture of PVC and AlCl3 as dopants. Molecular structure, morphology, optical, and electrical properties of PANI composite films were investigated by Fourier transform infrared spectroscopy, UVvis spectroscopy, four-probe method, and atomic force microscope. The results show that PANI film prepared by EBD has a similar molecular structure with initial powder. PVC is dehydrochlorinated under electron beam irradiation, but HCl fails to protonate the quinoid site of PANI during films deposition. AlCl3 doped in PANI films induces the decrease of surface resistance and the formation of a two-layered morphological structure in composite film. In addition, AlCl3 enhances the decomposition of PVC and increases the surface resistance of (AlCl3, PVC)-doped PANI composite film. POLYM. ENG. SCI., 2013. (c) 2012 Society of Plastics Engineers