N,N-Dimethylcarbamoyl(trimethyl)silane reacted with a series of α-ketoesters in anhydrous toluene at 60 ℃ to afford α-alkoxycarbonyl-α-siloxy amide derivatives in good yields (70%～99%). When the alkyl of α-ketoesters was L-2-isopropyl-5-methylcyclohexyl, the reactions possess stereo selectivity. The experimental results showed that the electronic property of the substituted group on the aryl ring affected both the reaction ratio and the yields of products. The structures of the products were characterized by element analysis, 1 H NMR, 13 C NMR and IR spectra. A reaction mechanism is proposed. The mild and no catalyst conditions, simple procedure, less byproducts and good yields provide an effective method for the preparation of α-alkoxycarbonyl-α-hydroxy amides.