A scalable cyanation of gem-difluoroalkenes to (hetero)arylacetonitrile derivatives was developed. This strategy features mild reaction conditions, excellent yields, wide substrate scope, and broad functional group tolerance. Significantly, in this reaction, aqueous ammonia offers a "N" source for the "CN" reagent and entirely avoids the use of toxic cyanating reagents or metal catalysis. Hence, we provide a green and alternative method for the synthesis of arylacetonitriles.