A direct correlation of the NHC ligand structure and the induced enantioselectivity has been uncovered for a series of new chiral gold(I) complexes. The Au(I)Cl complexes were identified by 1H, 13C NMR spectroscopy, and X-ray structure analysis. The corresponding activated Au(I) catalysts with a phenyl nitrile dynamic ligand are prepared and used in the catalysis of 1,6-enyne cyclization reactions. High chemical yields and good enantioselectivity have been obtained with 6%mol of the chiral NHC–Au(I) catalysts. The products in these reactions reach up to 75% ee. The structure of the chiral NHC ligand, where an ortho-biphenyl moiety is connected to the nitrogen atoms, the 3,5-dialkyl distal phenyl group plays a determining role in enantioselectivity.