Barium lithium fluoride nanocrystals were synthesized in cetyltrimethylammonium bromide (CTAB)/ 2-octanol/ water microemulsion systems. The impurity peaks in XRD patterns were not determined. The result of SEM confirmed that the average sizes and shape of the BaLiF3 nanocrystals. The formation of BaLiF3 and particles size were strongly affected by water content. With increasing water content and reaction times, the size of the particle increases. Meanwhile, the solvent was also found to play a key role in the synthesis of the BaLiF3 nanocrystals.