The promise of high specific energies for Li-O2 batteries has driven research toward the development of new compatible materials for this emerging technology. Obtained energies, however, fall short of the theoretical values partly due to parasitic chemistries arising from organic solvent decomposition during battery cycling. Electrolyte solvent and salt decomposition have also been identified as limiting factors for rechargeability of the battery. Although lithium trifluorosulfonamide (LiTFSI) dissolved in 1,2-dimethoxyethane (DME) has been shown to be a promising solvent/electrolyte candidate for Li-O2 batteries, significant challenges remain, namely minimizing decomposition of both the solvent and electrolyte salt during battery cycling. Herein, we provide spectroscopic labeling studies to identify the source of H2 at high potentials during charge and propose a decomposition pathway for DME to lithium formate and acetate products at low potentials. NMR studies were preformed to show that DME decomposes to lithium formate and acetate in aqueous Li2O2, products which are also observed after D2O workups on cathodes after discharge. Finally, we use density functional theory (DFT) to elucidate a mechanistic pathway for DME decomposition that is based on known organic oxidation processes. (Graph Presented).