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The CaF2–4LiF additive was added into SrTiO3 ceramics in order to decrease the sintering temperature for compact pulse power application. The crystalline structure, microstructure and energy storage performance of sintered ceramics were studied. Incorporating CaF2–4LiF additive to SrTiO3 ceramics contributes to a notably enhancement of the energy storage density. The great enhancement in energy storage density occurred due to the notable increase in breakdown strength and the refinement of microstructure. With 2 at% additive, the samples exhibited an average breakdown strength of 31.8 kV/mm, and an energy storage density of 1.212 J/cm3 which is about 1.4 times higher than pure SrTiO3.