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Metastable equilibrium solubilities and densities of the Li2SO4+K2SO4+Li2CO3+K2CO3+H2O system at 288 K were determined experimentally by using the isothermal evaporation method. According to the experimental data, the metastable equilibrium solubility phase diagram was constructed. In the phase diagram, there are three invariate( Li2CO3 ) has the smallest solubility in the quaternary system.