Solubilities, densities, and refractive indices in the (LiCl + CaCl2 + H2O) system at 273.15 K were determined using the isothermal dissolution equilibrium method. The phase diagram, density diagram, and refractive index diagram for this ternary system were drawn. The experimental phase diagram comprised three invariant points, four univariant solubility curves, and four crystallization areas corresponding to LiCl center dot 2H(2)O, LiCl center dot CaCl2 center dot 5H(2)O, CaCl2 center dot 4H(2)O, and CaCl2 center dot 6H(2)O. On the basis of the Pitzer model, the Pitzer mixing parameters and the solubility product constants (K-sp) of LiCl center dot 2H(2)O, LiCl center dot CaCl2 center dot 5H(2)O, CaCl2 center dot 4H(2)O, and CaCl2 center dot 6H(2)O were obtained. Then, the solubilities of this ternary system were calculated. A comparison shows that the calculated solubilities are in good agreement with the experimental results.