The crystallization in glasses is a paradoxical phenomenon and scarcely investigated. This work explores the non-isothermal crystallization of a multicomponent alumino-borosilicate glass via in situ high-energy synchrotron X-ray diffraction, atomic pair distribution function, and Raman spectroscopy. Results depict the crystallization sequence as Ca3Al2O6 and CaSiO4 followed by LiAlO2 with the final compound formation of Ca3B2O6. These precipitations occur in a narrow temperature range and overlap, resulting in a single exothermic peak in the differential scanning calorimetry thermogram. The concurrent nucleation of Ca3Al2O6 and CaSiO4 is intermediated by their corresponding hydrates, which have dominantly short-range order. Moreover, the crystallization of LiAlO2 and Ca3B2O6 is strongly linked with the changes of structural units during the incubation stage in non-isothermal heating. These findings clarify the crystallization of multicomponent glass, which have been inferred from ex situ reports but never evidenced via in situ studies.