In this work, we report a simple dip coating method to grow a thin polydopamine (PDA) layer on the surface of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) nano-fibers as the composite separator for application in high-safety lithium-ion batteries. A thin adherent PDA film uniformly distributed on the surface of PVDF-HFP nano-fibers, formed a unique core-shell structure. Compared with pure PVDF-HFP nonwoven membrane, the PDA coating PVDF-HFP composite membrane (PVDF-HFPPDA) not only exhibits much higher thermal stability, but also shows enhanced mechanical strength and tensile strength, which are very important for the assemble and long-term performance of the batteries. The ionic conductivity of the PVDF-HFP-PDA composite membrane is 1.40 mS cm(-1) which is much higher than 0.80 mS cm(-1) of the polypropylene (PP) separator. The lithium-ion batteries with PVDF-HFPPDA composite membrane show excellent cyclic stability and good rate performance. The PVDF-HFP-PDA composite membrane is suitable for applications in secondary lithium-ion batteries due to its advantages mentioned above. (C) 2016 Elsevier B.V. All rights reserved.