Processes, systems, and techniques for multivalent ion desalination of a feed water use an apparatus that has a cathode, an anode, and an electrodialysis cell located between the cathode and anode. The cell has a product chamber through which the feed water flows, a multivalent cation concentrating chamber on a cathodic side of the product chamber through which the concentrated multivalent cation solution flows, and a multivalent anion concentrating chamber on an anodic side of the product chamber through which the concentrated multivalent anion solution flows. The product chamber and the multivalent cation concentrating chamber are each bounded by and share a cation exchange membrane, and the product chamber and the multivalent anion concentrating chamber are each bounded by and share an anion exchange membrane. A monovalent ion species is added to at least one of the concentrated multivalent cation solution and the concentrated multivalent anion solution.