This study investigates the mass transfer mechanisms and the performance of membrane electrodialysis (ED) for regenerating lithium chloride (LiCl) solution commonly used in liquid desiccant dehumidification systems. Experiments were conducted using an ED experimental system while numerical simulation was performed using COMSOL Multiphysics. The results showed that the water flux transfer due to osmosis and electro-osmosis during ED regeneration of LiCl liquid desiccant was significant and could not be ignored. The water flux due to osmosis and electro-osmosis is directly associated with the osmotic gradient and the applied current between the cathode and anode, respectively. The average flux of water from the spent solution to the regenerated solution decreased from 0.292 to 0.161 g/s m2 when the initial concentration of the solutions in the spent and regenerated tanks increased from 18 to 30% (wt/wt) with the same applied current of 12 A and the same solution flow rate of 100 L/h. On the other hand, the salt flux due to osmosis was insignificant. The average salt flux transfer was 0.0053 g/s m2 when the initial concentration difference between the regenerated and the spent channels was 25% (wt/wt). Simulations were conducted to elucidate the relationship between the concentration profile of LiCl solution along the membrane surface and the concentration polarization in the ED channel with respect to the circulation flow rate and applied current. Overall, the results suggest that the concentration difference between the regenerated and spent LiCl solutions should be minimized for an optimum ED performance.