Efficient direct gem-difluoromethylenation of an sp³-hybridized carbon center in benzyl bromides using benzo-1,3-azolic (oxa-, thia- or aza-) difluoromethyl bromides for construction of a CH₂–CF₂ linkage has been developed through radical/radical C–C cross-coupling via two separate single electron transfer processes (SET) under the promotion of different copper sources.