Abstract Asymmetric hydroboration of simple and unactivated terminal alkenes (α-olefins), feedstock chemicals derived from the petrochemical industry, has not been efficiently realized for past decades. Using a bulky ANIPE ligand, we achieved a rare example of highly enantioselective copper-catalyzed Markovnikov hydroboration of α-olefins. The chiral secondary alkylboronic ester products were obtained in moderate to good yields and regioselectivities with excellent enantioselectivities. 1 Introduction 2 Conditions Optimization 3 Substrate Scope 4 Application 5 Mechanistic Discussion 6 Conclusions and Future Directions