Highly capacitive nano-Ni(OH)(2) spontaneously grows on the surface of a freshly cut graphite electrode (FGE) dipped in a NiCl2 aqueous solution. The obtained nano-Ni(OH)(2)/FGE composite electrode, free of binders and other additives, shows a high specific capacitance of similar to 1850 Fg(-1) in 30 wt% KOH solution. Both capacity and cycling stability of the Ni(OH)(2)/FGE can be improved by electrochemical (cathodic) polarization enhanced self-assembling. The nano-Ni(OH)(2) was supposed to be self-assembled on FGE, where a doped nano-scale active water film incurs the formation of Ni(OH)(2). The results described here provide a facile and low-cost pathway to produce highly capacitive Ni(OH)(2) and Ni(OH)(2)/FGE composite electrode used for energy storage. (C) 2013 Elsevier Ltd. All rights reserved.