Recent studies have shown that many aprotic electrolytes used in lithium-air batteries are not stable against superoxide and peroxide species formed upon discharge and charge. However, the stability of polymers often used as binders and as electrolytes is poorly understood. In this work, we select a number of polymers heavily used in the Li-air/Li-ion battery literature, and examine their stability, and the changes in molecular structure in the presence of commercial Li 2 O 2 . Of the polymers studied, poly (acrylonitrile) (PAN), poly(vinyl chloride) (PVC), poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride-cohexafluoropropylene) (PVDF-HFP), and poly(vinyl pyrrolidone) (PVP) are reactive and unstable in the presence of Li 2 O 2 . The presence of the electrophilic nitrile group in PAN allows for nucleophilic attack by Li 2 O 2 at the nitrile carbon, before further degradation of the polymer backbone. For the halogenated polymers, the presence of the electron-withdrawing halogens, and adjacent alpha and beta hydrogen atoms that become electron-deficient due to hyperconjugation makes PVC, PVDF, and PVDF-HFP undergo dehydrohalogenation reactions with Li 2 O 2 . PVP is also reactive, but with much slower kinetics. On the other hand, the polymers poly(tetrafluoroethylene) (PTFE), Nafion ® , and poly(methyl methacrylate) (PMMA) appear stable against nucleophilic Li 2 O 2 attack. The lack of labile hydrogen atoms and the poor leaving nature of the fluoride group allows for the stability of PTFE and Nafion ® , while the methyl and methoxy functionalities in PMMA reduce the number of potential reaction pathways for Li 2 O 2 attack in PMMA. Polyethylene oxide (PEO) appears relatively stable, but may undergo some crosslinking in the presence of Li 2 O 2 . Knowledge gained from this work will be essential in selecting and developing new polymers as stable binders and solid or gel electrolytes for lithiumair batteries.