Abstract The enantioselective introduction of gem ‐difluorinated carbonyl (i. e. α , α ‐difluoro carbonyl) moieties into organic structures is a synthetically valuable but highly challenging approach. During the past decades, continuous efforts have been made for the developments of synthetic strategies for constructing C( sp 3 )−CF 2 COR chiral centers with high levels of enantioselectivities. This review summarizes and discusses the recent advance in the enantioselective construction of gem ‐difluorinated carbonyl moieties, which are organized according to the reaction categories.