Degradation products of lithium oxygen batteries with a tetraethylene glycol dimethyl ether (TEGDME) electrolyte solution during discharge/charge cycles were monitored by an online cold trap pre-concentrator-gas chromatography/mass spectroscopy system in real time. A total of 37 peaks were detected and 27 of them were assigned to specific molecules. Degradation compounds were generated and decomposed in very complex manners during discharge/charge cycles. Most molecules were generated during charge as a result of the degradation of TEGDME by active oxygen species and/or electrochemical oxidation. These molecules generated during charge were decomposed during discharge by active oxygen species.