In this work, we present an exclusive study on the effect of Ferric chloride (FeCl3) on the electrical conductivity and characterizations of polyethylene oxide (PEO)/polyvinyl chloride (PVC)/polyaniline (PAni) conductive films. The objective of this paper is to improve the electrical conductivity of PEO/PVC/PAni conductive films with the addition of ferric chloride (FeCl3) as oxidants. PEO/PVC/PAni conductive films and PEO/PVC/PAni-FeCl3 conductive films were examined based on electrical conductivity, scanning electron microscopy (SEM) and Fourier transform infrared (FTIR). It is shown that the electrical conductivity of PEO/PVC/PAni conductive films increased with increasing PAni loading and further increased with the introduction of FeCl3. The SEM images reveal PAni agglomerations in the PEO/PVC matrix at higher PAni loadings. Lastly, the structures of the conductive films with the effect of PAni, FeCl3 were revealed by the FTIR study.