During the development of new composition versions for basic systems immobilizing high-level radioactive waste, the investigation of physico-chemical peculiarities has been carried out for various glass-ceramic materials, synthesized by the quench method from melts of the Na2O – Cs2O – CaO (SrO, BaO) – Al2O3 – B2O3 – SiO2 system with high zirconium content. Factors that determine solubility and zirconium retention have been studied, as well as homogeneity of the synthesized materials. The influence of zirconium upon the phase composition of materials, formation of their structure, crystallization processes, density values, and thermal properties have been considered. The obtained data point at possibilities in application of the chosen glass-forming system with the investigated combination of components in the field of synthesis of matrix materials for immobilization of high-level radioactive waste with high zirconium content.