Phase equilibria determination for the Al + Fe(II) + Mg + Ca + K + Cl + H2O system showed that FeCl2 is effective to promote the salting-out crystallization of AlCl3 center dot 6H(2)O. A novel process to recover AlCl3-6H(2)O from fly ash by salting-out crystallization with FeCl2 is proposed and proven feasible. This novel process includes leaching of fly ash by hydrochloric acid, reduction of Fe3+ to Fe2+, salting-out crystallization of AlCl3 center dot 6H(2)O with FeCl2, and filtering followed by washing. The solubility of AlCl3 center dot 6H(2)O in the Fe(II) + Mg + Ca + K + Cl + H2O system was determined over the entire practical concentration range and from 283.2 to 363.2 K using a dynamic method. The experimental solubilities were regressed to obtain new mixed solvent electrolyte (MSE) model parameters. These new parameters were capable of accurately representing the experimental data of the system from 283.2 to 343.2 K. The phase diagram of the ternary AlCl3-FeCl2-H2O system at 298.2 and 333.2 K was successfully constructed with the aid of the new MSE model parameters Based on the phase diagram, a promising route to recover AlCl3 center dot 6H(2)O by salting-out crystallization with FeCl2 was generated and verified to be feasible in laboratory experiments. All the results generated from this study will provide fundamental data for industrial applications aiming at the recovery of alumina from fly ash resources.