Lithium aluminum titanium phosphate (LATP)/polyacrylonitrile (PAN) composite fiber-based membranes were prepared by electrospinning dispersions of LATP particles in PAN solutions. The electrolyte uptakes of the electrospun LATP/PAN composite fiber-based membranes were measured and the results showed that the electrolyte uptake increased as the LATP content increased. The lithium ion conductivity, the electrochemical oxidation limit and the interface resistance of liquid electrolyte-soaked electrospun LATP/PAN composite fiber-based membranes were also measured and it was found that as the LATP content increased, the electrospun LATP/PAN composite fiber-based membranes had higher lithium ion conductivity, better electrochemical stability, and lower interfacial resistance with lithium electrode. Additionally, lithium//1 M LiPF(6)/EC/EMC//lithium iron phosphate cells using LATP/PAN composite fiber-based membranes as the separator demonstrated high charge/discharge capacity and good cycle performance. (C) 2011 Elsevier Ltd. All rights reserved.