Copper(II) triflate effectively catalyzes the reaction of (trimethylsilyloxy)acrylic esters and acetals to form γ-alkoxy-α-keto esters. The reaction proceeds under mild conditions providing products in good to excellent yields. The substrate scope was investigated, and it was demonstrated that the products could be converted into related compounds such as γ-hydroxy-α-keto esters and α-oximes.