Readily prepared chiral bis(imidazoline) NCN pincer iridium(III) complexes have been developed as the new and highly stereoselective catalysts for the direct asymmetric addition of terminal alkynes to trifluoropyruvates. With a catalyst loading of 5 mol%, a variety of optically active α-trifluoromethylated tertiary propargylic alcohols were thus produced in good yields with high enantioselectivity (27 examples, 74-96% ee). Both enantiomers of the catalysis products were obtained by using enantiomeric Ir(III) catalysts. In addition, gram scale synthesis of the product and its transformation to a potentially very useful 2H-1,2,3-triazole compound were accomplished. Control experiments suggested that the alkynylide Ir(III) intermediates were involved in the reactions.