Hybrid polymer dry electrolytes comprised of poly(ethylene oxide) (PEO), polyacrylonitrile (PAN), and LiClO4, were investigated. The impedance spectroscopy showed that the effect of PAN on the ion conductivity of PEO-based electrolytes depends on the concentration of lithium salt. When the mole ratio of lithium to oxygen is 0.062 (15%LiClO4-PEO), adding PAN will increase the ionic conductivity. Differential scanning calorimetry, NMR, and IR data suggested that the enhanced conductivity was due to both the decreasing of the PEO crystallinity and increasing of the degree of ionization of lithium salt. There was obviously no interaction between PAN and lithium ions, and PAN acts as a reinforcing filler, and hence contributes to the mechanical strength besides reducing the crystallinity of the polymer electrolytes. When the LiClO4-PEO-PAN hybrid polymer electrolyte was heated at 200 degrees C under N-2, PAN crosslinked partially, which further decreased the crystallinity of PEO and increased the ionic conductivity, and at the same time prevented the recrystallization of PEO upon sitting at ambient environment. (c) 2005 Wiley Periodicals, Inc.