Three-dimensional (3D) Co3O4 nanoclusters were fabricated with the assistance of tetrasodium ethylene diamine tetraacetic acid (EDTANa(4)) through a one-pot wet-chemical reaction, featuring self-limiting assembly of building blocks and controlled regrowth process. The molar ratio of Co2+ and EDTANa4 plays a key role in building initial clusters as blocks, and the amount of NaOH effects the regrowth process. A possible formation mechanism for the Co3O4 nanoclusters was proposed based on the characterization results of X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). The designed hierarchical Co3O4 nanoclusters exhibit a high specific capacitance of 221 F g(-1), at a current density of 2 A g(-1), in 2 mol L-1 KOH electrolyte. (C) 2017 Elsevier Inc. All rights reserved.