Anion exchange membranes are an important component in alkaline electrochemical energy conversion and storage devices, and their alkaline stability plays a crucial role for the long-term use of these devices. Herein, a systematic study was conducted for the analysis of polymer backbone chemical stability in alkaline media. Nine representative polymer structures including poly(arylene ether)s, poly(biphenyl alkylene)s, and polystyrene block copolymers were investigated for their alkaline stability. Polymers with aryl ether bonds in their repeating unit showed poor chemical stability when treated with KOH and NaOCH3 solutions, whereas polymers without aryl ether bonds [e.g., poly(biphenyl alkylene)s and polystyrene block copolymers] remained stable. Additional NMR studies and density functional theory (DFT) calculations of small molecule model compounds that mimic the Chemical structures of poly(arylene ether)s confirmed that electron-withdrawing groups near to the aryl ether bonds in the repeating unit accelerate chemical degradation. Results from this study suggest that the use of all carbon-based polymer repeating units polymers not bearing aryl ether-bonds) can enhance long-term alkaline stability of anion exchange membranes in electrochemical energy devices.