The long-term operation of Li-O2 batteries under full discharge/charge conditions is investigated in a glyme-based electrolyte. The formation of stable interfacial layer on the electrode surface during the initial cycling stabilizes reaction products at subsequent cycling stages as demonstrated by quantitative analyses of the discharge products and the gases released during charging. There is a quick switch from the predominant formation of Li2O2 to the predominant formation of side products during the first few cycles. However, after the formation of the stable interfacial layer, the yield of Li2O2 in the reaction products is stabilized at about 33-40%. Extended cycling under full discharge/charge conditions is achievable upon selection of appropriate electrode materials (carbon source and catalyst) and cycling protocol. Further investigation on the interfacial layer, which in situ forms on air electrode, may increase the long-term yield of Li2O2 during the cycling and enable highly reversible Li-O2 batteries required for practical applications.