A new allylnickel(II) complex ([S(R)]-N-[(1S)-2-(diphenylphosphino)-1-phenylethyl]-2-methyl-2-propanesulfinamide)(2,2,2-trifluoroacetato-κO)(π-allyl)nickel (2) was designed and prepared by using chiral phosphine. 2 was revealed to efficiently initiate the polymerization of l- and d-N-(1-(dodecylamino)-1-oxopropan-2-yl)-4-(propa-1,2-dien-1-yloxy)-benzamide (l-1 and d-1) in a living/controlled chain growth manner. Polymerization kinetics of l-1 and d-1 indicated that l-1 preferentially polymerized over the antipode d-1 by a factor of 1.9. In block copolymerization of rac-1 using the poly-l-150 as the macroinitiator, the polymerization proceeded in enantiomer-selective manner. It was found that enantiomeric excess (ee) value of the recovered monomer increased with the monomer conversion and finally reached to the maximum of 34%. These results suggest this chiral phosphine complex exhibits enantiomer-selectivity for the polymerization of chiral allene derivative monomer.