Gem‐difluoroethylene moiety holds pivotal roles in drug research owing to its unique ability as a bioisostere of the carbonyl group. Here, magnesium‐mediated reductive defluorinative cross‐electrophile coupling of α‐trifluoromethyl styrene with carbon‐centered electrophiles was developed. This method featured readily accessible reagents, mild conditions, and wide substrate scope, enabling the efficient production of gem‐difluoroallyl carboxylic acid and ketones. The establishment of this protocol will offer a general alternative for the acquisition of gem‐difluoroethylene compounds.