Alkaline anion exchange membranes (AAEMs) are an important component of alkaline exchange membrane fuel cells (AEMFCs), which facilitate the efficient conversion of fuels to electricity using nonplatinum electrode catalysts. However, low hydroxide conductivity and poor long-term alkaline stability of AAEMs are the major limitations for the widespread application of AEMFCs. In this paper, we report the synthesis of highly conductive and chemically stable AAEMs from the living polymerization of trans-cyclooctenes. A trans-cyclooctene-fused imidazolium monomer was designed and synthesized on gram scale. Using these highly ring-strained monomers, we produced a range of block and random copolymers. Surprisingly, AAEMs made from the random copolymer exhibited much higher conductivities than their block copolymer analogs. Investigation by transmission electron microscopy showed that the block copolymers had a disordered microphase segregation which likely impeded ion conduction. A cross-linked random copolymer demonstrated a high level of hydroxide conductivity (134 mS/cm at 80°C). More importantly, the membranes exhibited excellent chemical stability due to the incorporation of highly alkaline-stable multisubstituted imidazolium cations. No chemical degradation was detected by 1 H NMR spectroscopy when the polymers were treated with 2 M KOH in CD 3 OH at 80°C for 30 d.alkaline anion exchange membrane | trans-cyclooctene | block and random copolymer | cross-linked polymer | transmission electron microscopy A lkaline anion exchange membranes (AAEMs) are a class of polymer electrolytes constructed from immobilized cations with hydroxide counteranions (1-3). AAEMs have been widely used for a variety of electrochemical applications, such as redox flow batteries, electrodialysis, and water electrolysis (4-7). One of the most important applications for AAEMs is their use as polyelectrolytes in alkaline exchange membrane fuel cells (AEMFCs). These devices can efficiently convert chemical energy in fuels (e.g., H 2 , hydrazine, and direct alcohols) into electricity. In comparison with proton exchange membrane fuel cells and aqueous alkaline fuel cells, AEMFCs are advantageous because they allow for rapid reduction of oxygen at the cathode, limit fuel cross-over, prevent the formation of carbonate precipitates, and are compatible with nonnoble electrocatalysts (8-12). Because of their essential role in AEMFCs, AAEMs have been extensively studied to optimize their performance and, in particular, to improve their hydroxide conductivity and alkaline stability.Hydroxide conductivity is one of the most important parameters used to evaluate AAEMs, because it is directly related to the ohmic resistance and power density of an AEMFC (9). There are several strategies to enhance the hydroxide conductivity of AAEMs. The most straightforward method is to increase the ion exchange capacity (IEC), such that more ions are present in AAEMs. However, a higher IEC typically results in higher water uptake. While the presence of water facilitates h...