Abstract Microwave dielectric ceramics have drawn intensive interests in recent years due to the advanced development in communication area. High‐permittivity dielectric ceramics have thus become the highlight owing to dielectric ceramics with high permittivity could meet the demand of electronic components in both stabilization and miniaturization features. Bi 2 (Li 0.5 Ta 1.5 )O 7 shows its great potential among various high‐permittivity dielectric ceramics with a suitable permittivity and a considerable quality factor. Based on previous studies, a series of rational optimizations were conducted on Bi 2 (Li 0.5 Ta 1.5 )O 7 to manipulate the temperature coefficient of resonant frequency (TCF) and the sintering temperature for potential Low Temperature Co‐fired Ceramic (LTCC) applications. Two distinguished ceramics were obtained, Bi 2 (Li 0.5 Ta 1.5 )O 7 –0.03Bi 2 O 3 (sintering temperature of 850°C, ε r ∼ 64.1, Qf ∼ 8510 GHz, TCF—25.3 ppm/°C) and Bi 2 [(Li 0.5 Ta 1.5 ) 0.975 Ti 0.05 ]O 7 –0.015Bi 2 O 3 (sintering temperature of 980°C, ε r ∼ 66.2, Qf ∼ 10 950 GHz, TCF—8.5 ppm/°C). Dielectric resonator antenna (DRA) simulation was subsequently conducted and proved the ceramics holding excellent potential for microwave applications.