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A novel lead-free, high dielectric constant, ultra-wide temperature stable dielectric ceramic Ba 1−x Bi x Ti 1−x −y Zn 0.75x W 0.25x+y O 3+y (0.22≤x≤0.30, y=0.015) was synthesized by the traditional solid-state reaction method. The phase composition, electric and dielectric properties of the Ba 1−x Bi x Ti 1−x −y Zn 0.75x W 0.25x+y O 3 ceramics were investigated. The P-V-L dielectric theory was introduced. And, the chemical bond energy was calculated to track the changes in micro-structure. The relationships between chemical bond energy and the macroscopic dielectric properties(ε r , dielectric stability and dielectric loss ) in Ba 1−x Bi x Ti 1−x−y Zn 0.75x W 0.25x+y O 3+y ceramics were discussed systematically. Owing to the inhomogeneous micro-structure and the diffusion in phase transition, Ba 1−x Bi x Ti 1−x−y Zn 0.75x W 0.25x+y O 3+y ceramics showed a stable permittivity (~800±15%) over a ultra-wide temperature range (−30 to 375 °C). Moreover, dielectric loss was less than 0.02 and the insulation resistance was over 10 12 Ω cm. These features suggested that the Ba 1−x Bi x Ti 1−x−y Zn 0.75x W 0.25x+y O 3+y ceramic could be considered as a promising candidate material for energy storage applications in harsh environment. [ABSTRACT FROM AUTHOR]