Barium ions react with HF in aqueous media, forming BaF2 center dot HF for >0.7 wt.% aqueous HF instead of the expected BaF2 precipitates. Optimal yields of BaF2.HF have been obtained with the use of concentrated Ba(NO3)2 (0.8 M) and HF (26.0 M) aqueous solutions, using more than 2 equiv. of the latter. The composition, morphology and particle size of the formed precipitates are dependent upon the synthetic conditions, such as concentrations of starting materials, their stoichiometry and order of addition. BaF2 center dot HF is an excellent precursor for the preparation of optical fluoride ceramics having high transparency in the 0.3-12 u,m range, and scintillator ceramics (e.g., BaF2 or BaF2:Ce3+) as well. (C) 2013 Elsevier Ltd. All rights reserved.