Electrochemical behavior of layered LiNi0.5Mn0.5O2 in LiNO3 aqueous solution and its cyclic fading mechanism in electrolytes with different pH values were investigated. CV results show that LiNi0.5Mn0.5O2 has good electrochemical reversible behaviors in 5 mol/L LiNO3 solution. Meanwhile, the electrode in 5 mol/L LiNO3 with pH value of 12 demonstrates the best electrochemical stability. Based on the electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) results, it is proposed that suppressed charge-transfer resistance is the major reason, which is probably ascribed to the more stable electrode surface and less structure change.