Amine/Pd(II) cooperative catalysis has enabled a highly enantioselective addition of cyclic ketones to unactivated alkenes. The hallmark of the strategy includes amide-directed, regioselective activation of alkenes by Pd(II) and enhancing the nucleophilicity of α-carbon of the ketones by enamine catalysis to synergistically drive the reaction, which is basically unable to be accessed by a single catalyst. The combination of a commercially available Pd(II) catalyst and diphenylprolinol was able to provide the γ-addition products with good to high yields and efficient stereochemical control (up to 95% ee).