The effect of ethylene dimethacrylate (EDMA) as a surface modifier and polyaniline (PAni) loading on poly(vinyl chloride) (PVC)/poly(ethylene oxide) (PEO) matrix was investigated. PVC/PEO conductive composite films with different PAni loading were fabricated using solution casting technique. The inclusion of EDMA exhibited higher tensile strength, modulus of elasticity and electrical properties for all filler loadings of PVC/PEO/PAni conductive composite films. The scanning electron microscopy (SEM) morphology indicated that the inclusion of EDMA in conductive films provided decent fillers dispersion in the PVC/PEO phases. The structural modifications, if occurred, will be interpreted with the assistance of FTIR spectroscopy.