Herein, we report a highly efficient organocatalytic asymmetric synthesis of axially chiral biaryl phosphonates with p-quinone phosphonates and 2-naphthols via CPA-catalyzed asymmetric arylations. A series of chiral biaryl monophosphonates were obtained in excellent yields and enantioselectivities (up to 99% yield and 95% ee). This reaction could be operated at a gram scale with a low catalyst loading (0.5 mol %). Remarkably, our approach provides a green and ready access to chiral biaryl monophosphorus ligands. Compound 4ca was successfully converted to novel chiral biaryl monophosphorus ligands 7a, 7b, and 8 with high enantioselectivities in three steps.