Lithium triethylborohydride was found to promote the generation of α,α-difluoroenolates from 2-iodo-2,2-difluoroacetophenones, and applied to the synthesis of polyfluorinated β-hydroxy ketones via self-condensation or aldol reaction. The reaction indicates an unprecedented utilization of lithium triethylborohydride and provides novel access to the generation of α,α-difluoroenolates.