Abstract This study investigates the influences of the evaporation temperature and Mg 2+ concentration on the crystallization of an ammonium sulfate mother liquor. Specifically, their effects on the solubility, metastable zone width, crystallization amount, average particle size, and coefficient of variation of ammonium sulfate are examined through the laser and evaporation crystallization methods. Results show that solubility increases and the metastable zone width narrows with an increase in the evaporation temperature. At an evaporation temperature of 338.15 K, the controllability of the crystallization process improves and explosive nucleation does not easily occur. In this case, crystals with large average particle sizes, regular morphologies, and high crystallinity are obtained. With an increase in the Mg 2+ concentration in the solvent, solubility decreases. The added Mg 2+ covers the active nucleation sites, thus hindering the nucleation of ammonium sulfate and widening the metastable zone width. At a Mg 2+ concentration of 0.9 g L −1 or higher, Mg 2+ covers the active surfaces of the grains. This inhibits normal crystal growth and hinders the nucleation and growth of ammonium sulfate crystals, so the crystallization amount of ammonium sulfate significantly reduces.