A BaF₂ hollow nest-like nanostructure has been successfully synthesized, for the first time, via a facile sonochemical route from aqueous solution using EDTA as complexing reagent and CTAB as surfactant. Reaction conditions, such as concentrations of complexing reagent and surfactant, were found to have a close relation to the morphologies of final products. The ultrasound-induced self-assembly growth procedure has been proposed for the possible formation mechanism. The BaF₂ hollow structures showed enhanced photoluminescence compared to the solid structure.