A novel composite microporous polymer electrolyte based on poly(vinylidene fluoride), poly(ethylene oxide), and microporous molecular sieves ZSM-5 (denoted as PVDF-PEO/ZSM-5) was prepared by a simple phase inversion technique. PEO can obviously improve the pore configuration, such as pore size, porosity, and pore connectivity of PVDF-based microporous membranes, results in a high room temperature ionic conductivity. Microporous molecular sieves ZSM-5 can further improve the mechanical strength of PVDF-PEO blends and form special conducting pathway in PVDF-PEO matrix by absorb liquid electrolyte in its two-dimensional interconnect channels. The high room temperature ionic conductivity combined with good mechanical strength implies that PVDF-PEO/ZSM-5 based composite microporous polymer electrolyte can be used as candidate electrolyte and/or separator material for high-performance rechargeable lithium batteries. (c) 2006 Elsevier B.V. All rights reserved.