Hydrophilic fumed Silica (SiO2)/polyacrylonitrile (PAN) composite electrolyte membranes were prepared by electrospinning composite solutions of SiO2 and PAN in N,N-dimethylformamide (DMF). Among electrospinning solutions with various SiO2 contents, the 12 wt% SiO2 in PAN solution has highest zeta potential (-40.82 mV), and exhibits the best dispersibility Of SiO2 particles. The resultant 12 wt% SiO2/PAN nanofiber membrane has the smallest average fiber diameter, highest porosity, and largest specific surface area. In addition, this membrane has a three-dimensional network structure, which is fully interconnected with combined mesopores and macropores because of a good SiO2 dispersion. Composite electrolyte membranes were prepared by soaking these Porous nanofiber membranes in I M lithium hexafluorophosphate (LiPF6) in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 vol%). It is found that 12 wt% SiO2/PAN electrolyte membrane has the highest conductivity (1.1 x 10(-2) S cm(-1)) due to the large liquid electrolyte uptake (about 490%). In addition, the electrochemical performance of composite electrolyte membranes is also improved after the introduction Of SiO2. For initial cycle, 12 wt% SiO2/PAN composite electrolyte membrane delivers the discharge capacity of 139 mAh g(-1) as 98% of theoretical value, and still retains a high Value of 127 mAh g(-1) as 89% at 150th cycle, which is significantly higher that of pure PAN nanofiber-based electrolyte membranes. (C) 2009 Elsevier Ltd. All rights reserved.