Well-defined nanostructures of the cobalt oxide are designed intensively to pursue large surface area and high conductivity as the electroactive material for supercapacitors (SCs). Instead of merely fabricating effective electroactive materials, two kinds of the cobalt oxide nanostructures synthesized directly on nickel foam to achieve good contact between the material and the substrate are compared to clarify the growth mechanism and the structure-dependent SC performance. The nanobrushes are completely composed of nanoparticles while the rhombus nanopillars present integrated structure by the recrystallization of single nanopillars. A higher specific capacitance (C-F) of 509 F/g is obtained for the SC electrode with CoO rhombus nanopillar array at a scan rate of 10 mV/s, comparing to that of 169 F/g for the CoO nanobrush array-based SC electrode, due to the larger electroactive surface area and less recombination sites for the former case. The C-F value is enhanced by 38% as compared with the initial value after 3000 cycles of repeated charge/discharge process for the CoO rhombus nanopillar array-based SC electrode due to the activation of the material. The results provide a blue print for achieving highly efficient SC electrode by carefully designing the well-established electroactive material to attain facile and long-lasting faradic reactions. (C) 2016 Elsevier B.V. All rights reserved.