A ligand-controlled regiodivergent Cu-catalyzed aminoboration of unactivated terminal alkenes with diboron reagents and hydroxylamines has been developed. The xantphos-ligated CuCl complex guides the boron and amino groups to the terminal and internal positions, respectively. On the other hand, the opposite regioisomers are selectively obtained under the N-heterocyclic carbene-based IPrCuBr catalysis. The two Cu catalysts can readily transform simple and abundant terminal alkenes into highly valuable beta-borylalkylamines regiodivergently.