Developing highly ion conductive and desirable electrodialysis (ED) performance anion exchange membranes (AEMs) is of great significance. In this work, we report a strategy for fabricating novel AEMs based on a series of fluoro-methyl poly(arylene ether ketone) s having long-side-chain imidazolium groups for ED. Having hydrophilic conductive flexible side-chain imidazolium groups and rigid hydrophobic backbone within AEM matrix, the optimized AEM (PAEK-60-im) shows low water uptake of 24.9% at 80 degrees C and desirable ion conductivity of 22.01 mS cm(-1) at 30 degrees C. In NaCl removal application of ED, PAEK-60-im shows the NaCl removal ratio of 69.66% within 120 min, outperforming commercial AEM-Type II (68.98%). Accordingly, it has a higher current efficiency of 83.7% but lower energy consumption of 5.9 kWh kg(-1), compared with the commercial one (82.0%; 6.6 kWh kg(-1)). In particular, in selectrodialysis application, possibly owing to the synergistic effect of pore-size sieving effect resulting from macro-separation morphology and hydration energy difference of SO42- ions (-1000 kJ mol(-1)) and Cl- ions (-317 kJ mol(-1)) in feeding solution, PAEK-60-im shows significantly superior monovalent anion perm-selectivity (Cl-/SO42-) of 7.70 at 30 min, relative to commercial anion-selective Neosepta ACS (5.27) and many other reported mono-valent anion selective AEMs having elegant surface modified layers. The superior ED performance of the homogeneous PAEK-60-im is suggestive of its potential separation application.