The effects of Nd2O3 addition on the crystallinities, microstructures, and properties of MgO–Al2O3–SiO2 (MAS) glass‐ceramics are investigated. The experimental results show that the addition of Nd2O3 allows complete sintering densification of the MAS at lower temperatures, and appropriate addition ratios increase the crystallinity, promote the formation of Indialite, improve the MAS microstructure, reduce the coefficient of thermal expansion, and optimize the dielectric properties. Ultimately, the best performance is achieved by adding 4 wt% Nd2O3 to the MAS sample and sintering at 1255 °C for 15 min. The bulk density is 2.51 g cm−3, εr = 6.50, tanδ = 1.96 × 10−3 (13 GHz), and CTE = 4.621 ppm °C−1.