Morphology of electroactive materials in electrodes affects their electrochemical performance and capacity of energy storage devices. New architectures (3D) for electrodes and cells will overcome the traditional electrodes’ problems. However, preparation of 3D electrodes needs complex, multi-step and high-cost processes. We prepared nickel oxide (NiO) hollow nano-fiber electrodes with the combination of the electrospinning and eletroless plating techniques and evaluated their performance as electrodes for electrochemical capacitors. Non-woven mats with poly(methyl methacrylate) (PMMA) nano-fibers were prepared by electrospinning technique. Then the PMMA mats were immersed in the Ni electroless plating bath and the Ni-plated PMMA fibers were heated at 550°C, 4h to remove the PMMA. The average outer diameter of the NiO hollow nano-fibers is 3 um and inside is 0.67 um. EDX analysis of the heat treated mats suggests that the follow fibers contain nickel oxide (NiO) with some phosphorous compounds and the PMMA in the mats as a mold is removed completely. The cyclic voltammograms for the NiO hollow nano-fiber electrode in the aqueous solution (1 M KOH) indicate that the electrode is electrochemically active. The estimated capacity of the NiO hollow fiber electrode from the voltammograms is 190.5 F g-1 (per gram of NiO).