As one of the most typical and promising membrane processes, electrodialysis (ED) technique plays a more and more significant role in industrial separation. Especially, the separation of monovalent cations and multivalent cations is currently a hot topic, which is not only desirable for many industries but also challenging for academic explorations. The main aim of the present contribution is to view the advances of a wide variety of monovalent cation perm-selective membranes (MCPMs) and their preparation technologies including (1) covalent cross-linking, (2) surface modification, (3) polymer blending, (4) electrospinning, (5) nanofiltration alike membrane, and (6) organic-inorganic hybrid. The relevant advantages and disadvantages with respect to some specific cases have been discussed and compared in detail. Furthermore, we elaborately discuss the opportunities and challenges of MCPMs, the fabricating strategies to take and the future perspectives. (C) 2017 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.