With the rapid development of the microelectronics industry, many efforts have been made to improve glass-ceramics’ sinterability, thermal conductivity, and dielectric properties, which are essential components of electronic materials. In this study, low-alkali borosilicate glass-ceramics with PVA addition and glass-BN composites were prepared and successfully sintered at 770 °C. The phase composition, density, microstructure, thermal conductivity, and dielectric constant were investigated. It was shown that PVA addition contributes to the densification process of glass-ceramics (~88% relative density, with closed/open pores in the microstructure) and improves the thermal conductivity of glass material from 1.489 to 2.453 W/K.m. On the other hand, increasing BN addition improves microstructures by decreasing porosities and thus increasing relative densities. A glass-12 wt. % BN composite sample exhibited almost full densification after sintering and presented apparent and open pores of 2.6 and 0.08%, respectively. A high thermal conductivity value of 3.955 W/K.m and a low dielectric constant of 3.00 (at 5 MHz) were observed in this material. Overall, the resulting glass-ceramic samples showed dielectric constants in the range of 2.40–4.43, providing a potential candidate for various electronic applications.

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