Abstract An efficient kinetic resolution of binaphthyl triflates is developed via Ni-catalyzed asymmetric C(sp2)–P cross-coupling to access substituted atropisomeric phosphines. Moreover, the phosphine framework showed superior reactivity and enantiocontrol in Pd-catalyzed asymmetric allylic substitution. Mechanistic control experiments revealed that the introduction of a pyridine ring provides both optimal steric hindrance and a secondary coordination site, enabling the successful development of a new class of atropisomeric P,N-bidentate ligands, denoted as PMOP.