Poor stability of lithium metal anodes in liquid electrolytes hinders its practical application in rechargeable batteries with very high energy density. Herein, we present an approach to tackle the intrinsic problems of Li metal anodes from the standpoint of separators. By a facile and versatile method based on mussel-inspired surface chemistry, a hybrid polydopamine/octaammonium POSS (PDA/POSS) coating was spontaneously formed on the surface of PE separators through the self-polymerization and strong adhesion feature of dopamine. This ultrathin PDA/POSS coating endows PE separators with different surface characteristics while keeping its microporous structure almost unchanged. The altered surface characteristics influence the separator/electrolyte interaction, and lead to remarkable enhanced ionic conductivity (from 0.36 mS cm(-1) to 0.45 mS cm(-1)) and Li+ ion transference number (from 0.37 to 0.47) of PE separators as well as the improved stability of lithium/electrolyte interface, which effectively decreases the electrode polarization and suppresses the lithium dendrites formation, contributing to superior C-rates capability and cycling performance of cells. (C) 2017 Elsevier Ltd. All rights reserved.