Catalytic regioselective generation of an allyl-Cu complex through Cu-B(pin) (pin = pinacolato) addition to 1,3-dienes followed by reaction with an electrophilic cyanation reagent to afford multifunctional organoboron compounds is presented. Reactions of a wide range of 1,3-dienes with different substitution patterns promoted by an easily accessible phosphine-Cu complex proceed with high yields and regioselectivity.