A crucial parameter for the design and operation of electrodialysis (ED) units is the limiting current density (LCD). This is often identified with the diffusion-limited current density, which corresponds to the complete solute depletion in the layer adjacent to the membrane. Current-voltage curves obtained from measurements with electrodes in contact with the solution (i.e. without membranes) are consistent with this interpretation and exhibit a horizontal plateau identifying LCD. However, real ED systems show more complex behaviours, with a reduced-slope tract instead of a plateau and a third region in which the current increases more markedly (overlimiting current). The phenomena involved in the limiting region are not yet totally characterized and the determination of LCD in ED units is still ambiguous. In the present work, we explore the issues related to the identification of LCD, by measurements on ED units, assessing the influence of operating conditions and validating a simplified process simulator. A new method to determine LCD, based on the current efficiency, is proposed and compared with other methods presented in the literature. A second limiting quantity is also identified, i.e. the critical current density, below which diffusion phenomena prevail on migration and a method for its assessment is proposed.