A comprehensive study of the thermodynamic conditions (temperature, composition) of the existence of the cubic phase within the limits of homogeneity region in the quasi-binary PbF2-EuF3 system was carried out. Solid solution samples were obtained by solid-phase synthesis and co-precipitation technique from aqueous nitrate solutions. Phase equilibria were investigated in two regions: the solvus line in the range of 0-10 mol% EuF3 and the region of existence of the ordered rhombohedral R-phase in the range of 35-45 mol% EuF3. The structure of phases in the PbF2-EuF3 system was examined at temperatures below the phase transition temperature in lead fluoride (365°C). The possibility of obtaining a single-phase preparation of a cubic phase of high purity in 0-37 mol% EuF3 composition range has been demonstrated. The region of existence of the ordered rhombohedral R-phase in the concentration range from 37-39 to 43-44 mol% EuF3 was defined using X-ray phase analysis, optical probing, and Raman scattering.