An efficient approach for the reversal of regioselectivity in the nucleophilic introduction of difluorinated carbanion into α,β-enones has been developed via a silylium catalysis. The strong electron-withdrawing properties and bulky substituents of in situ-generated silyl triflic imide catalyst is the key for the 1,4-addition reaction to proceed smoothly. The synthetic utility is highlighted by the further use of this method for the synthesis of 2,4,6-triarylsubstituted 3-fluoropyridines in a one-pot manner.