A VO–flyash composite electrode for a lithium/polymer battery (LPB) was developed. We investigated XRD diffraction and electrochemical properties of vanadium oxide (VO)–flyash composite with polyvinylidene (PVDF)/polyacrylonitrile (PAN)-based polymer electrolyte as a function of mixing ratio. The discharge capacity of VO–flyash with 50wt.% V2O5 in PVDF–PAN–PC5EC5iClO4 electrolyte was 150 and 128mAh/g at 1 and 10 cycles, respectively. The discharge capacity of VO–flyash with 85wt.% V2O5 was 195mAh/g at 10 cycles. The capacity retention of VO–flyash anode with 3wt.% V2O5 was higher than that of VO–flyash cathode with 85wt.% V2O5. The VO–flyash with 3wt.% V2O5 composite anode in PVDF/PAN-based electrolyte shows good capacity with cycling.