The enantioselective synthesis of axially chiral 1-arylisoquinolines by rhodium-catalyzed [2+2+2]-cycloaddn. of 1,6-diynes and isoquinolinyl alkynes has been developed. The diphenylphosphinoyl-substituted axially chiral 1-arylisoquinolines, e.g., I, were successfully derivatized to the corresponding axially chiral P,N ligand and Lewis base catalyst. [on SciFinder(R)]