The objective of this research was to study the purification of industrial-grade phosphoric acid (P2O5) by conventional electrodialysis. The experiments were conducted using a three-compartment cell with anion and cation membranes, and industrial acid solution was introduced into the central compartment. The elemental analysis of the diluted solution indicated that the composition of magnesium, phosphates, and sodium was reduced in the central compartment. The ratios of the concentration of the ions and the phosphates were essentially unchanged by the process. Consequently, electrodialysis could not purify the acid in the central compartment, and the migration of phosphate ions to the anolyte produced a highly concentrated phosphoric acid solution containing sulfates and chlorides as impurities. However, the migration of the phosphate ions across the membrane consumed a large amount of energy. Detailed speciation diagrams were constructed in this study. These diagrams showed that metal-phosphate complexes were predominant in the industrial phosphoric acid solution. This result explains why the ratios of the concentrations of the ion metals and the phosphates did not change in the purification process. The energy consumed in the electrodialysis indicated that the metal-phosphate complexes were less mobile than the free-phosphate ions. The speciation diagrams explained the experimental results satisfactorily.