Hydrogen-bond-activated C–N bond cleavage of allylic amines was realized in Pd-catalyzed allylic alkylation to form the C–C bond product. The method could be expanded to a series of allylic amines and carbonyl compounds with excellent results. It provides a new and convenient access to C–C bond formation based on Pd-catalyzed allylic alkylation of allylic amines by using only inexpensive alcohol solvents.