With the development of 5G/6G communication, the requirements of portable devices for miniaturization and multifunction make low‐temperature co‐fired ceramic (LTCC) more and more important. In the area of high‐frequency high‐density passive integration, microwave dielectric ceramics with a low dielectric loss and high thermal conductivity are urgently needed to ensure the effective signals transmission and system reliability. However, most microwave dielectric ceramics with a low dielectric loss were not applicable for the LTCC technology due to the high sintering temperature. In this work, a series of MgO‐based ceramics [(100 − x) wt.% MgO–x wt.% (0.2SrF2–0.8LiF) (x = 5,7,10)] were prepared by solid‐state reaction method. The addition of sintering aid 0.2SrF2–0.8LiF (S2L8) decreased the sintering temperature below 880°C without degrading the microwave dielectric properties of ceramics. Microwave dielectric properties of ceramics, including quality factor Q × f, relative permittivity εr, and temperature coefficient of resonant frequency τf, were investigated to find the optimum composition and sintering temperature. In general, MgO–7 wt.% S2L8 ceramic sintered at 860°C exhibits outstanding properties of Q × f = 180 233 GHz, εr = 9.11, τf = −40.33 ppm/°C, and a high thermal conductivity of 24.02 W/(m K). This series of ceramics are suitable to be co‐fired with Ag electrodes. With all those great properties, this series of MgO‐based ceramics are expected to be the candidates for LTCC applications in 5G/6G technology.

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