The solid−liquid phase equilibria of the Ba 2+ //Cl − , S 2− , and OH − −H 2 O quaternary system and its three subternary systems at 298.15 K are studied via the isothermal solubility phase equilibrium method. The solubility data, liquid properties of density and pH, and phase diagrams of the ternary and quaternary systems are obtained. Solid species of Ba(OH) 2 •8H 2 O, BaCl 2 • 2H 2 O, Ba(OH)Cl•2H 2 O, and BaS exist in the quaternary system and corresponding ternary systems at 298.15 K. The four solid species build up two invariant points, one disproportionate and one proportionate, and four phase regions. The largest phase area is covered by Ba(OH)•8H 2 O, and the lowest water point is the proportionate invariant point saturated by BaCl 2 •2H 2 O, Ba(OH)Cl•2H 2 O, and BaS.