In this study, the phase diagram of the NaCl+RbCl binary system was measured using differential scanning calorimetry, and the measured molar percentages of the binary mixture RbCl ranged from 12 to 97 mol%, updating and extending the experimental data for this binary system. The liquid phase of this system was thermodynamically modeled using a modified quasichemical model, and a computer optimization program for evaluation of the experimental data on phase equilibria and other thermodynamic data was developed based on this model. All thermodynamic models of the NaCl+RbCl binary system were constructed; calculations of the phase diagram, enthalpy of mixing, and activity coefficient of NaCl of the NaCl+RbCl binary system were completed using the obtained model parameters; and the calculated eutectic point positions were xRbCl = 0.567 and 550.2 °C. The calculated results were able to reproduce the various types of experimental data well, and the thermodynamic self-consistency between different types of experimental data was demonstrated.