Based on the requirement of the new technology for producing Mg–N compound fertilizer by the reaction of MgCl 2 and (NH 4 ) 2 SO 4 , the phase equilibrium of the quaternary system Mg 2+ , NH 4 + //Cl − , SO 4 2− –H 2 O at 25 °C was studied. The solubilities of the quaternary system Mg 2+ , NH 4 + //Cl − , SO 4 2− –H 2 O were measured using isothermal method, and the phase diagram of this system was investigated. According to the phase diagram, there are nine solid phase crystalline zones, which correspond to MgSO 4 ·7H 2 O, MgSO 4 ·6H 2 O, MgSO 4 ·5H 2 O, MgSO 4 ·4H 2 O, (NH 4 ) 2 SO 4 , MgSO 4 ·(NH 4 ) 2 SO 4 ·6H 2 O, MgCl 2 ·6H 2 O, NH 4 Cl and MgCl 2 ·NH 4 Cl·6H 2 O respectively. MgSO 4 ·(NH 4 ) 2 SO 4 ·6H 2 O has the largest crystalline zone among these crystalline zones, which indicates that the double salt MgSO 4 ·(NH 4 ) 2 SO 4 ·6H 2 O is the easiest to crystallize out. Based on the analysis and calculation of the phase diagrams, the suitable conditions for the new technology were determined. The extended Pitzer model was derived and applied to the phase equilibrium calculation of system Mg 2+ , NH 4+ //Cl − , SO 4 2 –H 2 O and its sub-systems at 25 °C. The results showed that the calculated values were consistent with experimental results well. [ABSTRACT FROM AUTHOR]