Copper(I)-catalyzed asymmetric monoborylation of 1,3-dienes has been developed. We describe the production of either optically active homoallyl- or allylboronates with high regio- and enantioselectivity (88-97% ee) through monoborylation of 1,3-dienes. The reaction with 1,3-cyclohexadiene derivatives afforded the corresponding enantioenriched homoallyboronates. By simply changing the reaction conditions, a drastic change of product preference between homoallyl-and allylboronates was found in the reaction of 1,3-cyclopentadiene and 1,3-cycloheptadiene.