A new method for the generation of the “PhSO₂CF₂Cu” species from readily available difluoromethyl phenyl sulfone (PhSO₂CF₂H) has been developed. The “PhSO₂CF₂Cu” reagent can be applied in (phenylsulfonyl)difluoromethylation of arylboronic acids, which affords a convenient approach to introducing the PhSO₂CF₂ group into aromatics.