Chiral N,N'-dioxide-In(OTf)(3) complexes were developed as efficient catalysts to catalyze the vinylogous Mukaiyama aldol reaction of the silyl dienol ester with aldehydes. The corresponding delta-hydroxy-alpha,beta-unsaturated esters were obtained in up to 99% yield and 98% ee. Moreover, the obtained (R)-3v can be easily transformed to natural bioactive products.