Electrodeionization (EDI) is an electrically driven separations technology that employs ion-exchange membranes and resin particles. Deionization occurs under the influence of an applied electric field, facilitating continuous regeneration of the resins and supplementing ionic conductivity. While EDI is commercially used for ultrapure water production, material innovation is required for improving desalination performance and energy efficiency for treating alternative water supplies. This work reports a new class of ion-exchange resin-wafers (RWs) fabricated with ion-conductive binders that exhibit exceptional ionic conductivities—a 3–5-fold improvement over conventional RWs that contain a non-ionic polyethylene binder. Incorporation into an EDI stack (RW-EDI) resulted in an increased desalination rate and reduced energy expenditure compared to the conventional RWs. The water-splitting phenomenon was also investigated in the RW in an external experimental setup in this work. Overall, this work demonstrates that ohmic resistances can be substantially curtailed with ionomer binder RWs at dilute salt concentrations.