In this study, two novel microwave dielectric ceramics were designed and synthesized using the solid‐state reaction method based on the CaO–MoO3–La2O3 pseudo‐ternary phase diagram. The X‐ray diffraction (XRD) patterns and Rietveld refinement results indicate that pure phase microwave dielectric ceramics (CaLa2(MoO4)4 and Ca3MoO6) can be produced with CaO, MoO3, La2O3 ratios of 1, 1, 4, and 3, 1, 0, respectively. CaLa2(MoO4)4 shows the potential value for application in Low Temperature Co‐fired Ceramic technology. In addition, the Phillips–van Vechten–Levine theory, infrared reflectance spectrum, and THz time‐domain spectrum are used further to study the structure‐property relationship of the two ceramics. Finally, a 5G patch antenna used in Sub‐6 GHz communication technology was successfully designed and manufactured. The study of the relationship between chemical bonds and dielectric properties of the two ceramics, along with the development of the patch antenna, establishes a foundation for scientific research and practical applications in related ceramic systems.