The effect of additives of P2O5 on the solubility of molybdenum in the amorphous part of glass and on the phase composition of the crystallized part of the highly alkaline glasses of the Li2O–(Na2O–K2O)–B2O3-SiO2 system was studied. The comparison of the phase composition of samples with or without phosphorus prior and after annealing allowed to determine the change of solubility of molybdenum in the amorphous part of the samples and to evaluate the thermal stability of the synthesized glass-ceramic materials. It was found, that for the compositions without phosphorus and the samples without lithium, when molybdenum is added at the synthesis stage, almost all of the molybdenum is included only in the crystalline molybdates. The study has shown an increase in the solubility of molybdenum only in the structure of lithium-containing glasses with phosphorus.