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Transparent Bi2ZnOB2O6 glasses were prepared by melt quenching technique. The thermal behavior of the glasses was studied using differential thermal analysis (DTA), structure by X-ray diffraction (XRD) and the morphology is observed using scanning electron microscope (SEM) and optical polarization microscope. Crystallization kinetics has been studied under isothermal and non-isothermal conditions by using DTA. Two exothermic peaks were observed in the non-isothermal DTA curve and XRD analysis confirms that the first exothermic peak belongs to crystallization of β-BiB3O6 phase whereas the second exothermic peak belongs to formation of Bi2ZnOB2O6 phase. The obtained Avrami parameter indicates that the glass heat-treated at its first crystallization temperature leads to surface crystallization whereas the glass heat-treated at second crystallization temperature shows three-dimensional bulk crystallization. The glasses heated at intermediate temperatures of the exothermic peaks exhibit both the β-BiB3O6 and Bi2ZnOB2O6 phases indicating the presence of surface and bulk crystallizations. The glass morphological study also confirms the same behavior.