We confirmed the existence of LiO2 by electrochemical quartz crystal microbalance (EQCM) in TEGDME based Li-O2 batteries. Our results indicated that Li2O2 is generated through stepwise electrochemical reactions rather than disproportionation. We report for the first time that the formed Li2O2 oxidizes to LiO2 at relative negative potential and O2 at positive potential respectively. Our conclusions were based on both experimental observations and quantitative analysis. This may enlighten us to reconsider the Li-O2 batteries mechanisms in a quantitative way.