Electrotransport of sodium chloride near and through the ASV anion exchange membrane was first investigated. Chronopotentiometric and current-voltage characteristics results have shown that the ASV membrane acts as a totally conducting plane with respect to the transport of NaCl electrolyte. SEM and AFM images contributed to confirm the overall homogeneous surface of the membrane. Further chronopotentiometric studies of the membrane were evaluated in the presence of different alkaline chloride solutions in order to explore the influence of alkali co-ions on the transport phenomena. Membrane characterization led to determine the transport number of chloride counterion in the membrane. It is reported in this work that chronopotentiometry using the Sand equation toward the homogeneous ion exchange membrane is a simple and efficient method for determination of the diffusion coefficient of the electrolytes in the bulk solution. Discussions on the transport properties of the electrolyte solutions in relation with the hydrated ion sizes allowed us to verify the diffusion coefficient of the electrolytes determined by means of chronopotentiometric method.