Cu(i)-Catalyzed diastereoselective carboboration of α-alkyl-substituted α,β-unsaturated carboxylic esters to produce β-boryl-α-quaternary carbon esters was developed. The carbon skeletons of dialkyl sulfates, primary allyl halides, and benzyl bromides were transferred to the α-position of the substrates to provide products in moderate to good yields with a diastereoselectivity of >95% in most cases. Substrates bearing a β-(hetero)aryl substituent gave higher diastereoselectivities than those bearing a linear β-alkyl substituent. The crystal structure of the potassium trifluoroborate derivative shows that the reactions probably go through a copper(i) enolate intermediate and the diastereoselectivity arises from the electrophilic attack of electrophiles to the less hindered side of the enolates.