Catalytic asymmetric aldol reactions of silyl enol ethers with aldehydes (Mukaiyama aldol reactions) have been performed using novel chiral zirconium catalysts. The reactions proceeded in high yields under mild conditions, and anti-adducts were obtained in high diastereo- and enantioselectivities. The catalysts were first prepared from zirconium(IV) tert-butoxide (Zr((OBu)-Bu-t)(4)), (R)-3,3'-diiodo-1,1'-binaphthalene-2,2'-diol ((R)-3,3'-I2BINOL), a primary alcohol, and a small amount of water. It was revealed that the primary alcohol played an important role in completing the catalytic cycle and that a small amount of water was essential for obtaining high selectivities. Moreover, activities of the chiral zirconium catalysts were enhanced by using new ligands, (R)-3,3'-I-2-6,6'-X2BINOL (X = Br, I, C2F5), and it has been shown that even aldol reactions of less reactive substrates proceeded smoothly using the novel zirconium catalysts. Finally, NMR studies of these catalysts were performed, which suggested that the catalyst would form a dimeric structure and that the water affected the catalyst formation.