Comprehensive Summary Catalytic asymmetric hydrophosphination of unsaturated substrates has been proven to be one of the most straightforward ways to achieve chiral phosphine compounds. Although the methodologies of transition metals and organocatalysts catalyzed enantioselective hydrophosphination reactions have been well developed during the last decade, the enantioselective construction of quinoline and isoquinoline‐based phosphines remains challenging. Furthermore, the chiral quinoline‐based phosphines play a significant role in the preparation of chiral P,N ‐ligands. Herein, we report a comprehensive investigation for the asymmetric addition of diarylphosphine oxides to a wide range of α,β‐unsaturated quinolines and isoquinolines, catalyzed by commercial chiral phosphoric acid, affording the corresponding products with up to 99% yield and 98% ee.