During nuclear waste vitrification, loss of sodium (Na) and boron (B) occurs, as these elements are highly volatile at high temperatures, which causes fluctuations in composition and consequently affects the properties of the glass products. In this study, we investigated the volatilization behaviors of Na and B from a simulated high-level waste glass as functions of heating temperature and dwelling duration. Based on the data obtained regarding the composition of Na and B and the structure of the glass, a hypothetical model was proposed to explain the volatilization behaviors of Na and B from a structural viewpoint. As the loss of Na and B during vitrification, the crystallization of the glass occurred. Thus, the crystallization behavior of the simulated waste glass upon composition deviation was studied.