Vitrification is one of the best ways to immobilize high-level radioactive waste (HLW) worldwide over the past 50 years. Since the glass matrix has a medium (3.0-5.5 A) and short (1.5-3.0 A) periodicity, it can accommodate most elements from the periodic table. Borosilicate glass is the most suitable glass matrix for vitrification due to its high chemical durability, high waste-loading capacity, and good radiation resistance. Mo is a fission product contained in liquid waste generated in the process of reprocessing spent nuclear fuel and exists in the form of MoO4 2- in the glass. MoO4 2- forms a depolymerization region without directly connecting with the glass network former. When the concentration of Mo increases in the depolymerization region, it combines with nearby alkali or alkaline earth cations to form a crystalline molybdate phase. Phase separation and crystallization in the glass can degrade the performance of the material because it changes the physical and chemical properties of the glass. In particular, since alkali molybdate has high water solubility when it forms crystals containing radioactive elements such as Cs, there is a risk of leakage of radionuclides by groundwater during deep underground disposal. Therefore, in this study, the most stable glass-ceramic composition was developed using various alkali elements, and the difference in phase separation and crystallization behavior in glass and the stability of the solidified body were analyzed by structural analysis of the glass network and alkali molybdate. The cause of the difference in crystallization of alkali molybdate according to the type of alkali cation is structurally analyzed, and using this, research is conducted to increase the Mo content in the glass without crystallization.