A cooperative Cu/Pd-catalyzed asymmetric three-component reaction of styrenes, B-2(pin)(2), and allyl carbonates was reported. This reaction, in the presence of chiral CuOAc/SOP and achiral Pd(dppf)Cl-2 catalysts, occurs smoothly with high enantioselectivities (up to 97% ee). The allylboration products, which contain alkene (or diene) unite and alkylboron group, are easily functionalized. The utility of this protocol was demonstrated through the synthesis of an antipsychotic drug, (-)-predamol.