Glycol-mediated facile solvothermal process for synthesis of mesoporous cobalt ferrite (CoFe2O4) nanoparticles (NPs) is reported. The structure, surface functionalization and morphology of the prepared sample are characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and field emission scanning electron microscope (FESEM). The role of the electrolyte on the charge-storage performance of the CoFe2O4 NPs is investigated in detail by performing cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), electrochemical impedance spectroscopy (EIS) and cyclic stability tests in neutral (3M Na2SO4) and alkaline (3M KOH) aqueous electrolytes. The electrochemical activity of inverse spinel CoFe2O4 can be tuned with the electrolytes. It possesses specific capacitance (Csp) of 477 and 176 F/g in alkaline and neutral aqueous media respectively at a scan rate of 2 mV/s. The sample shows better performance in KOH electrolyte because of the smaller size of solvated ions whereas possesses better rate capability in the neutral electrolyte. Significant Coulombic efficiency of 97% is observed in alkaline medium with a rise in Csp upto 5,000 cycles, which remains constant until 10,000 cycles. © 2020 Curtin University and John Wiley & Sons, Ltd.