The electrochemical behavior of a commercial LiCoO2 with spherical shape in a saturated Li2SO4 aqueous solution was investigated with cyclic voltammetry and electrochemical impedance spectroscopy. Three redox couples at E-SCE = 0.87/0.71, 0.95/0.90 and 1.06/1.01 V corresponding to those found at E-Li/Li* = 4.08/3.83, 4.13/4.03 and 4.21/4.14V in organic electrolyte solutions were observed. The diffusion coefficient of lithium ions is 1.649 x 10(-10) cm(2) S-1, close to the value in organic electrolyte solutions. The results indicate that the intercalation and deintercalation behavior of lithium ions in the Li2SO4 solution is similar to that in the organic electrolyte Solutions. However, due to the higher ionic conductivity of the aqueous solution, current response and reversibility of redox behavior in the aqueous solution are better than in the organic electrolyte solutions, suggesting that the aqueous solution is favorable for high rate capability. The charge transfer resistance, the exchange current and the capacitance of the double layer vary with the charge voltage during the deintercalation process. At the peak of the oxidation (0.87 V), the charge transfer resistance is the lowest. These fundamental results provide a good base for exploring new safe power sources for large scale energy storage. (C) 2008 Elsevier Ltd. All rights reserved.