Ion-containing block copolymers continue to attract significant interest as conducting membranes in energy storage devices. Reversible addition鈥揻ragmentation chain transfer (RAFT) polymerization enables the synthesis of well-defined ionomeric A鈥揃C鈥揂 triblock copolymers, featuring a microphase-separated morphology and a combination of excellent mechanical properties and high ion transport. The soft central 鈥淏C鈥?block is composed of poly(4-styrenesulfonyl(trifluoromethylsulfonyl)imide) (poly(Sty-Tf2N)) with 鈭扴O2鈥揘鈥?/sup>鈥揝O2鈥揅F3 anionic groups associated with a mobile lithium cation and low-Tg di(ethylene glycol)methyl ether methacrylate (DEGMEMA) units. External polystyrene A blocks provide mechanical strength with nanoscale morphology even at high ion content. Electrochemical impedance spectroscopy (EIS) and pulse-field-gradient (PFG) NMR spectroscopy have clarified the ion transport properties of these ionomeric A鈥揃C鈥揂 triblock copolymers. Results confirmed that well-defined ionomeric A鈥揃C鈥揂 triblock copolymers combine improved ion-transport properties with mechanical stability with significant potential for application in energy storage devices.