A fast microwave-assisted synthesis method followed by a post-calcining process is used to prepare three-dimensional (3D) nanosphere-like NiCo2O4 nanostructure. The 3D NiCo2O4 nanospheres are constructed by intertwined two-dimensional (2D) ultrathin mesoporous nanosheets. The nanosphere-like NiCo2O4 has a large specific surface area (SSA, 146.5 m(2) g(-1)) and is successfully applied to electrocatalytic oxidation of methanol. Electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and chronoamperometry (CA) measurements are used to investigate electro-catalytic performance of the as-prepared NiCo2O4. The current density of NiCo2O4/Ni foam (NiCo2O4/NF) electrode in 1 M KOH with 0.5 M methanol is up to 40.9 A g(-1). And the current density can be returned to 97% of the original value by replacing new 1 M KOH electrolyte with 0.5 M methanol after a long-term CV cycle (500 cycles). These results show that our prepared NiCo2O4 possesses high electro-catalytic activity and good longterm stability for methanol oxidation. This may be benefit from the unique porous nanosphere-like structure and large SSA. (C) 2014 Elsevier B.V. All rights reserved.