Although methods for synthesizing chiral phosphorus scaffolds are available, the potential of this molecular chirality remains largely unexplored. Herein, we present a remote desymmetrization of prochiral biaryl phosphine oxides through an organocatalytic asymmetric arylation. This metal-free approach enables the efficient synthesis of a wide range of densely functionalized P(V)-stereogenic compounds with good to excellent yields and satisfactory enantioselectivities. Mechanistic studies reveal that hydrogen bonding and ion-pairing interactions are crucial for achieving precise stereocontrol in this transformation.