Chiral ligands 1-2 with L-prolinol backbone have been applied to the enantioselective phenylacetylene addition to aldehydes, providing chiral propargylic alcohols in high yields and moderate enantioselectivities. Only the ligand 1 in combination with Ti((OPr)-Pr-i)(4) afforded the products with opposite absolute configuration in significant enantiomeric excesses and high yields. The ratio of Ti((OPr)-Pr-i)(4) to the ligand had great influence on the enantiomeric excess of the product. (c) 2005 Elsevier B.V. All fights reserved.