We herein describe a highly diastereoselective rhodium(I)-catalyzed C−F bond functionalization of gem-difluoroalkenes with arylboronic acids. In contrast to previously developed Pd(II)-and Pd(0)-catalyzed methods, the Rh(I)/BINAP catalytic system enabled the C−F bond arylation of both trisubstituted β,βdifluorostyrenes and tetrasubstituted β,β-difluoroacrylates in >99:1 dr toward the synthesis of valuable monofluoroalkenes. Experimental and computational studies suggested a plausible migratory insertion/β-F elimination mechanism with the [Rh(I)-Ar] species.