Abstract Perovskite-type barium lithium fluoride (BaLiF 3) was synthesized by pyrolysis of metal trifluoroacetates. The reaction temperature necessary for producing a single-phase material was found to be 600°C, which was lower than that for a conventional solid-state reaction or a melting method. Eu-doped BaLiF 3 was also prepared and characterized to examine the suitability of trifluoroacetates for precursors in synthesizing homogeneous complex metal fluoride materials. It was demonstrated that trivalent Eu 3+, which was used as acetate for a starting material, was reduced to divalent Eu 2+ in the pyrolysis process of BaLiF 3, as indicated by a broad blue emission due to an allowed 4 f 65 d→4 f 7 transition at 408 nm with a ultraviolet excitation at 254 nm. The concentration quenching of the blue emission occurred at 5 at% of Eu in BaLiF 3, indicating that Eu was homogeneously dispersed in the BaLiF 3 host lattice. Mechanisms of the formation and reduction process of BaLiF 3 were discussed based on pertinent chemical reactions.