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The demand for high-performance grinding wheels is gradually increasing due to rapid industrial development. Vitrified bond diamond composite is a versatile material for grinding wheels used in the backside grinding step of Si wafer production. However, the properties of the vitrified bond diamond composite are controlled by the characteristics of the diamond particles, the vitrified bond, and pores and are very complicated. The main objective of this study was to investigate the effects of SiO2–Na2O–B2O3–Al2O3–Li2O–K2O–CaO–MgO–ZrO2–TiO2–Bi2O3 glass powder on the sintering, microstructure, and mechanical properties of the vitrified bond diamond composite. The elemental distributions of the composite were analyzed using electron probe micro-analysis (EPMA) to clarify the diffusion behaviors of various elements during sintering. The results showed that the relative density and transverse rupture strength of the composite sintered at 620 °C were 91.7% and 126 MPa, respectively. After sintering at 680 °C, the glass powder used in this study exhibited a superior forming ability without an additional pore foaming agent. The relative density and transverse rupture strength of the composite decreased to 48.2% and 49 MPa, respectively. Moreover, the low sintering temperature of this glass powder protected the diamond particles from graphitization during sintering, as determined by X-ray diffraction and Raman spectrum. Furthermore, the EPMA results indicate that Na diffused and segregated at the interface between the diamond particles and vitrified bond, contributing to the improved bonding. The diamond particles can remain effectively bonded by the vitrified bond even after fracture.