Enantioenriched P-stereogenic phosphines have served as important chiral ligands for transition metals as well as organocatalysts. However, they are less studied compared to their counterparts that have chiral carbon backbones, in part due to their less availability and synthetic challenges. catalytic asymmetric synthesis of P-stereogenic phosphines has attracted broad attention during the past decades. Transition-metal-catalyzed asymmetric allylic substitution reactions have led to tremendous achievements in synthetic organic chemistry, serving as a powerful strategy to construct C−C and C−X bonds with chiral carbon centers. A nickel-catalyzed asymmetric allylation of secondary phosphine oxides for the synthesis of tertiary phosphine oxides was realized with high enantioselectivity. The dynamic kinetic asymmetric transformation of SPO was accomplished in the presence of nickel complex.