Different salt types have different effects on the liquid water content of saline soil, resulting in differences in the physico-mechanical properties and water/salt migration process of saline soil. In order to investigate the phase transition process and the change of the liquid water content in composite saline soil, saline soils with the same total salt content and different ratios of sodium chloride and sodium sulfate were taken as the objects. The results indicated that two phase transitions occur in the saline soil with single salt type, while three phase transitions can be found in the composite saline soil with two salt types. Mirabilite crystallization contributes to the 1st phase transition, mirabilite and ice precipitate together in the 2nd phase transition process, and mirabilite, ice, and hydrohalite precipitate simultaneously in the 3rd phase transition process. The liquid water is reduced in the phase transition process during cooling, and the pore characteristic has been changed significantly. The change of the liquid water content reflects the processes of salt crystallization and ice formation in saline soil, then the amounts of ice and hydrated salt were calculated at different temperatures, and the mechanism of inhibiting the deformation of sulfate saline soil was examined by adding sodium chloride. The results have reference value for those seeking understanding of the deformation in natural composite saline soil, and these findings can provide theoretical basis for the phase transition mechanism of saline soil in cold regions.