Enantiomerically pure sulfinimines as important building blocks in the asymmetric synthesis of amine derivatives are prepared in good to excellent yields from chiral p-toluenesulfinamide with aromatic, heteroaromatic, and aliphatic aldehydes. The unprecedented feature of the reported procedure is that the formation of the sulfinimines was achieved by the catalytic action of Yb(OTf)(3) in THF at room temperature. The reaction conditions were also applicable to Ellman's sulfinimines.