Sulfonated poly(phthalazinone ether ketones) (SPPEK) with ion exchange capacities from 0.77 to 1.82 mmol·g-1 are synthesized via an electrophilic substitution reaction. Nuclear magnetic resonance and infrared absorption spectroscopy are used to characterize the chemical structure of the obtained polymers for confirming the successful introduction of sulfonic groups. SPPEKs show excellent thermal stability; their temperature required to achieve 5% weight loss is about 360 °C. Accordingly, the obtained membranes possess high ion perm-selectivity, proton conductivity, and low area resistance. Regarding the electrodialysis-related performance of the membranes, the SPPEK-4 membrane has the highest limiting current density (39.8 mA·cm2), resulting from its high content of sulfonic groups. In a desalination test of standard solution, SPPEK-3 and SPPEK-4 membranes exhibit both better salt removal rate and acceptable energy consumption than commercial membrane. Additionally, SPPEK-3 membrane shows outstanding performance in terms of high concentration rate and low energy consumption during saline water treatment, which indicates the feasibility of novel membranes in electrodialysis application.