NiCo2O4 and NiMnxCo2-xO4-y (x <= 1.0) have been synthesized by a co-precipitation method, and the effects of Mn substitution for Co on the microstructural and electrochemical properties pertaining to the supercapacitor applications have been studied. Spinel structure is retained when a quarter of Co of the spinel is substituted with Mn (i.e., x=0.5), where the Mn ions predominantly occupy the octahedral sites of the spinet lattice. The presence of Mn significantly suppresses crystal growth upon thermal treatment but tends to cause severe crystallite agglomeration. Electrodes of the materials exhibit nearly ideal electrochemical capacitor behavior in neutral electrolyte solution (1 M KCl(aq)). Mn substitution greatly enhances the specific capacitance of the spinel, giving gravimetric and superficial specific capacitances of ca. 110 F g(-1) and ca. 380 mu F cm(-2), respectively for x=0.5 powder. The capacitance enhancement is attributed to the facile charge-transfer characteristic of the Mn ions, as revealed by in situ X-ray absorption near-edge structure analysis. (C) 2012 Elsevier Ltd. All rights reserved.