Transparent optical ZnO–Bi2O3–B2O3 (ZBB) glass-ceramics were created by the melt quenching technique. In this work, a melt of the glass containing stoichiometric ratios of Zn/Bi/B and As was studied. Differential scanning calorimeter (DSC) measurements was used to measure the thermal behavior. VIS/NIR transmission measurements were used to determine the transmission window. X-ray diffraction (XRD) was used to determine crystal phase. In this study, we explore new techniques and report a detailed study of in-situ XRD of the ZBB composition in order to correlate nucleation temperature, heat treatment temperature, and heat treatment duration with induced crystal phase.