A novel category of polyphenylene oxide/high-impact polystyrene (PPO/HIPS) alloy was used as the polymer matrix (abbreviated as mPPO) and loaded with different volume fractions (0, 10, 20, 30, 40, 50 vol.%) of MgTiO₃–Ca0.7La0.2TiO₃ (abbreviated as MTCLT) ceramics to prepare composites by injection molding. Its micromorphology, density, dielectric, thermal and mechanical properties were analyzed in detail. The experimental results show that the composites possess a compact microstructure because HIPS increases the fluidity of PPO. Due to the excellent dielectric properties of both mPPO and MTCLT, the composites have an extremely low dielectric loss. The realization of the high ceramic filler fraction greatly limits the thermal expansion of the polymer chain by introducing the interphase, so that the coefficient of thermal expansion of the composite material could be as low as 21.8 ppm/∘C. At the same time, the presence of ceramic particles could reinforce the mechanical property of the composites. When the ceramic filler fraction is higher than 20 vol.%, the bending strength of the composite material is around 110 MPa. When the ceramic filler fraction is 40 vol.%, the composite possesses the best comprehensive performance. The dielectric constant is 6.81, the dielectric loss is 0.00104, the thermal expansion coefficient is as low as 25.3 ppm/∘C, and the bending strength is 110.4 MPa. Due to its excellent properties, this material can be a good candidate in the field of microwave communication.A novel category of polyphenylene oxide/high-impact polystyrene (PPO/HIPS) alloy was used as the polymer matrix (abbreviated as mPPO) and loaded with different volume fractions (0, 10, 20, 30, 40, 50 vol.%) of MgTiO₃–Ca0.7La0.2TiO₃ (abbreviated as MTCLT) ceramics to prepare composites by injection molding. Its micromorphology, density, dielectric, thermal and mechanical properties were analyzed in detail. The experimental results show that the composites possess a compact microstructure because HIPS increases the fluidity of PPO. Due to the excellent dielectric properties of both mPPO and MTCLT, the composites have an extremely low dielectric loss. The realization of the high ceramic filler fraction greatly limits the thermal expansion of the polymer chain by introducing the interphase, so that the coefficient of thermal expansion of the composite material could be as low as 21.8 ppm/∘C. At the same time, the presence of ceramic particles could reinforce the mechanical property of the composites. When the ceramic filler fraction is higher than 20 vol.%, the bending strength of the composite material is around 110 MPa. When the ceramic filler fraction is 40 vol.%, the composite possesses the best comprehensive performance. The dielectric constant is 6.81, the dielectric loss is 0.00104, the thermal expansion coefficient is as low as 25.3 ppm/∘C, and the bending strength is 110.4 MPa. Due to its excellent properties, this material can be a good candidate in the field of microwave communication.