The intercalation/deintercalation characteristics of electrochemically formed Ni(OH)(2)/Ni/ITO electrodes in aqueous KOH and nonaqueous LiPF6 + EC:DEC (1:1) electrolyte solutions were studied. The Ni(OH), film was grown by Ni electrodeposition and a subsequent anodizing process. The metallic Ni nano-layer between Ni(OH)(2) and ITO was identified by X-ray photoelectron spectroscopy (XPS). To understand the characteristics of the Ni(OH), film, the intercalation and deintercalation of OH- ion in KOH and Li+ in LiPF6 + EC:DEC (1:1) electrolyte were investigated using cyclic voltammetry and charge calculations and further confirmed with the structure, oxide states and interfacial properties of the Ni(OH)(2) layer using X-ray diffraction, atomic force microscopy, scanning electron microscopy, XPS, ac impedance spectroscopy, and in situ transmittance spectroscopy. The Ni(OH)(2)/Ni/ITO electrode showed improved interfacial properties due to the metallic Ni nano-layer when it was compared with directly electrodeposited Ni(OH)(2)/ITO.