A series of novel P-chiral monophosphorus ligands exhibit efficiency in asymmetric Suzuki鈥揗iyaura coupling reactions, enabling the construction of an array of chiral biaryl products in high yields and excellent enantioselectivities (up to 96% ee) under mild conditions. The carbonyl-benzooxazolidinone moiety in these chiral biaryl products allows facile derivatization for further synthetic applications. A computational study has revealed that a 蟺鈥撓€ interaction between the two coupling partners can enhance the enantioselectivity of the coupling reaction.