A highly efficient copper-catalyzed asymmetric addition of terminal alkynes to isatins has been developed. In the presence of a catalytic amount of copper iodide and a chiral phosphine ligand, the reaction gave the corresponding chiral 3-alkynyl-3-hydroxyindolin-2-ones in high yields with high enantioselectivity. This methodology has a broad substrate scope, and the synthetic utility of the present protocol was further demonstrated by the transformation of chiral alkynylation products.