Poly(vinylidene fluoride) (PVDF) is a semi-crystalline thermoplastic polymer with excellent thermal stability, electrochemical stability and corrosion resistance, which has been widely studied and applied in industrial nonmetallic heat exchanger and piezoelectric-film sensor. In this study, polyaniline (PANI) nanofibers were synthesized using dodecylbenzene sulfonic acid as the surfactant. The obtained PANI nanofibers were blended in PVDF matrix to enhance thermal conductivity and tensile strength of composite materials. Electric field was applied for the orientation of membrane structure during membrane formation. Scanning electron microscope (SEM ) images exhibited that the PANI nanofibers were well-dispersed in the composite membranes. The structure of composite membranes was more orderly after alignment. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) indicated that the content of PANI nanofibers contributed to the transformation of PVDF from alpha-phase to beta-phase. Both the tensile strength and thermal conductivity of composite membranes were significantly improved. This tendency was further enhanced by the application of electric field. The maximum tensile strength was obtained when the content of PANI nanofibers was 3 wt%, which was 46.44% higher than that of pure PVDF membrane. The maximum thermal conductivity of composite membranes after alignment was 84.5% greater than that of pure PVDF membrane when the content of PANI nanofibers was 50 wt%. The composite membrane is a promising new potential material in heat transfer field and the mechanism explored in this study would be informative for further development of similar thermal conductive polymeric materials. (C) 2018 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.