An enantioselective hydrophosphination of alkenyl isoquinolines is developed by using a copper-chiral diphosphine ligand catalyst. It provides a direct and atom-efficient approach to prepare a variety of chiral phosphines with an isoquinoline unit in good yields and high enantioselectivities. In addition, these chiral phosphine products are useful bidentate P,N-ligands which showed potential application in asymmetric catalysis.