An efficient nickel-catalyzed stereoselective asymmetric intramolecular reductive coupling of N-1,6-alkynones is reported. A P-chiral monophosphine ligand AntPhos was found to be a privileged catalyst for constructing versatile functionalized chiral pyrrolidine rings using triethylsilane as the reducing reagent. Concise synthesis of pyrrolidines with chiral tertiary allylic alcohols was achieved in high yields (99%), excellent stereoselectivity (>99:1 E/Z), and enantioselectivity (>99:1 er) with very broad substrate scope. Totally, thirty-five N-1,6-alkynones were synthesized and applied in this reaction successfully. This reaction can be scaled up to gram scale without loss of its enantioselectivity. Ligand effects and reaction mechanism are investigated in detail. While the developed asymmetric synthesis of pyrrolidine with chiral tertiary allylic alcohols is anticipated to find wider applications in organic synthesis and chemical biology, the discovered new reactions of N-1,6-alkynone with AntPhos using different catalyst systems would further expanded its new research fields and attract more detailed explorations in the future.