Dielectrics with high permittivity and temperature stability are important for the development of high-temperature multilayer ceramic capacitors (MLCCs). In this study, Ca[Formula: see text]NaxTi[Formula: see text]NbxSiO5 (abbreviated as CTS[Formula: see text]NN) ceramics were prepared by solid-phase reaction method. The introduction of NN weakens the long-range ordered displacement of Ti, leading to a significant increase in the dielectric temperature stability. The CTS−2%NN samples exhibit high permittivity (53) and TCC [Formula: see text] ppm/∘C in the range of [Formula: see text]C to 300∘C. The CTS-based ceramics behave high dielectric temperature stability. In addition, the bandgap of the CTS-based ceramics increased significantly, which is favorable for improving the breakdown strength of the material. For [Formula: see text]% samples, the breakdown strength reaches 621[Formula: see text]kV/cm. Thus, the designed CTS-based dielectrics are promising for high-temperature capacitors.