The catalytic enantioselective fluorination of α-cyanoalkylphosphonates catalyzed by chiral palladium complexes was examined. Treatment of α-cyanoalkylphosphonates with N-fluorobenzenesulfonimide as the electrophilic fluorinating reagent under mild reaction conditions afforded the corresponding α-fluorinated α-cyanoalkylphosphonates in excellent yields with high enantiomeric excesses (80-91%).