Electrospinning is a versatile method for the preparation of submicron fibers under ambient temperature. We demonstrate a new approach based on this method for preparing an electrode which consists of fibers coated with metal oxide particles on their surface. The electrochemical characterization of the electrode was performed and compared with those of the conventional metal oxide film electrode. We prepared nickel oxide (NiO)/polymer fibrous electrodes by electrospinning technique. The capacitance of the as-prepared NiO/polymer fibrous electrode in 1 mol l(-1) KOH aqueous solution was 5.8 F g(-1) (per gram of NiO). Heat treatment (at 150 degrees C for 1 h in the air) of the NiO/polymer fibrous electrode enhanced the capacitance of the NiO/polymer fibrous electrode. The capacitance of the heat treated NiO/polymer fibrous electrode was 187 F g(-1) (per gram of NiO).