The coking biochemical effluents including aeration biological filter effluent and reverse osmosis concentrated water were desalted by electodialysis, in which ions transfer, wastewater desalination, ion exchange membrane fouling were examined in the experiments. The results showed that two types of coking wastewater were suitable to be desalted by electrodialysis, in which the transfer and removal of different ions were related to ion concentration and ionic radius. It was showed by the measurement of membrane resistance that the fouling of different ion exchange membranes had different properties in the electrodialysis system of different coking wastewater. SEM and IR analyses showed that, the anion exchange membrane fouling was resulted from the organic compounds contained in the aeration biological filter effluent. The granular inorganic fouling mainly appeared in the concentrated sides of electrodialysis in the reverse osmosis concentrated water desalination. Moreover, the concentrated side fouling of cation exchange membrane was more obvious than that of anion exchange membrane.