In contrast to typical grafted anion exchange membranes (AEMs), a novel graft type AEM owning flurocarbon side chains and quaternized ammonium aromatic backbone was developed by a controlled atom transfer radical polymerization (ATRP) reaction. The experimental results revealed this kind of structure facilitated the formation of robust and long connective ion transport channels. Thus, the resulting AEM (IEC = 1.35 mmol/g) exhibited a relatively high hydroxide conductivity of 44 mS/cm, although its water uptake was below 30% (at 30 °C). Simultaneously, this AEM also displayed fascinating mechanical strength and alkaline stability. A H₂/O₂ fuel cell test using incorporated fluorocarbon grafted AEMs yielded a peak power density of 85 mW/cm² at a current density of 150 mA/cm²; this will be improved on development of a chemical compatible fluorine-based alkaline ionomer as ionic polymer binder in the electrodes' catalyst layers.