In this work, we demonstrate a facile layer-by-layer (LBL) self-assembly method for controllable preparation of single-, double-, and triple-shelled NiO hollow nanospheres by calcining Ni(OH)(2)/C precursors formed at different stage. It is observed that the external nanoflakes of the NiO hollow nanospheres are inherited from the Ni(OH)(2) precursors organized on the surface of carbon spheres via a self-assembly growth process and the inner shells result from the formation of different Ni(OH)(2) layers within the carbon spheres during different preparation cycles. Supercapacitive performance of the three types of NiO hollow nanospheres as active electrode materials has been evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge. The results indicate that double-shelled NiO hollow nanosphere sample with largest surface area (92.99 m(2) g(-1)) exhibits the best electrochemical properties among the three NiO hollow nanosphere samples. It delivers a high capacitance of 612.5 F g(-1) at 0.5 A g(-1) and demonstrates a superior long-term cyclic stability, with over 90% specific capacitance retention after 1000 charge-discharge cycles. This excellent performance is ascribed to the short diffusion path and large surface area of the unique hollow structure with nanoflake building blocks for bulk accessibility of faradaic reaction. (C) 2013 Elsevier B.V. All rights reserved.