To effectively improve the affinity of polyethylene (PE) separators with liquid electrolyte without causing a serious pore blockage and to develop a more suitable technology for the industrial production process, porous polyvinylidene fluoride (PVDF) layer-coated PE separators are prepared by the dip-coating method followed by a dry-cast process. Different from previous investigations, a less volatile solvent and a relatively volatile nonsolvent are used to yield a preferable pore structure. A brief introduction on the pore formation mechanism during the dry-cast process is provided. The pore structure of coating layer is found to be successfully controlled by changing evaporation temperature, nonsolvent content, and PVDF concentration. The porous PVDF coating layer-modified separators show better affinity with liquid electrolyte and thermal stability. Especially, the ionic conductivity of the modified separator/liquid electrolyte system with a suitable porous coating layer on the separator could reach two times as that of PE separator/liquid electrolyte system, and the cell assembled with modified PE separator shows better cycle performances. This modification process is proved to be a facile, controllable, and effective method for PE separator modification. Meanwhile, this work could provide some theoretical and technical guidance for the production process. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41036.