Abstract Electrodialysis (ED) is an alternative to the conventional thermal regeneration of high-salt solutions used in air conditioning systems (ACSs). In this work, a simplified mathematical model was developed to describe the solute and water transport. The solute hydration number and free water content were proposed to characterize the solute hydration properties. A laboratory-scale ED regeneration system was set up to investigate the regeneration performance of three kinds of high-salt solutions (aqueous LiCl, LiBr and CaCl2 solutions) at various initial concentrations and current densities. The results demonstrate good agreement between numerical and experimental findings. The initial concentration and applied current density have great impacts on ED performance. Firstly, higher initial concentration generally results in lower membrane permselectivity, current efficiency, solute and water transfer rate, and higher energy consumption. Secondly, higher current density has a positive effect on solute and water transport but leads to more energy consumption. The solute hydration number and free water content both decrease with increasing initial concentration. The appropriate mass concentrations of 15%, 25% and 15% are respectively suggested for aqueous LiCl, LiBr and CaCl2 solutions when applying ED in ACSs to ensure responsible performance.