In this study, polydopamine (PDA) coated electrospun poly(vinyldiene fluoride) (PVDF) nanofibrous membranes used as separator for lithium-ion batteries are successfully prepared. Their morphology, chemical and electrochemical characterization are investigated. The morphology and porosity measurements of the membranes show that the PDA coating does not harm to the structure of the electrospun PVDF nanofibrous membranes. Due to the PDA coating, it makes the PVDF surface hydrophilic and thus increases the electrolyte uptake and ionic conductivity, resulting in the enhanced performance of batteries. The battery using the PDA coated PVDF nanofibrous separator exhibits better cycling performance and higher power capability than that the battery using the bare PVDF nanofibrous separator. This study underlines that the PDA-coating treatment provides a promising process for the fabrication of advanced electrospun nanofibers separator in the lithium-ion battery applications.