Fabricating stable mono-/multi-valent anion-selective membranes with high perm-selectivity for electrodialysis (ED) applications is critical but challengeable. In this work, we have fabricated a series of novel homogeneous monovalent anion-selective amphoteric ion-exchange membranes (AIEMs, PAES-im-Xc) based on a long-side-chain type imidazolium-functionalized poly(arylene ether sulfone) cross-linked with 4,4'-diazostilbene-2,2'-disulfonic acid disodium salt (DAS) for ED. By tuning the mass percent of DAS added, low swelling ratio but appreciably high anion perm-selectivity (in Cl-/SO(4)(2-)system) of optimized AIEM are achieved to values of 8.0% and 47.12 at current density of 2.5 mA cm(-2), respectively. In particular, at an enhanced current density of 5.0 mA cm(-2), its perm-selectivity reaches 12.5, significantly outperforming commercial monovalent anion-selective Neosepta ACS (5.27). The appreciably high perm-selectivity possibly arises from pore-size sieving effect from dense matrix structure with cross-linkings and strong electrostatic repulsion between negative fixed -SO3- groups and negative divalent ions of SO42- in feeding solution. The superior performances might be particularly interesting findings that can facilitate the development of advanced mono-/bi-valent anion-selective membranes in applications of sea water desalination, resource recovery and water treatment/pretreatment etc..