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Hierarchical porous metal oxides arrays is critical for development of advanced energy storage devices. Herein, we report a facile template-assisted electro-deposition plus glucose decomposition method for synthesis of multilayer CoO/C hollow spheres arrays. The CoO/C arrays consist of multilayer inter-connected hollow composite spheres with diameters of ～350 nm as well as thin walls of ～20 nm. Hierarchical hollow spheres architecture with 3D porous networks are achieved. As cathode of high-rate hybrid batteries, the multilayer CoO/C hollow sphere arrays exhibit impressive enhanced performances with a high capacity (73.5 mAh g?1 at 2 A g?1), and stable high-rate cycling life (70 mAh g?1 after 12,500 cycles at 2 A g?1). The improved electrochemical performance is owing to the composite hollow-sphere architecture with high contact area between the active materials and electrolyte as well as fast ion/electron transportation path.