A tandem oxidative α-hydroxylation/β-acetalization reaction of β-ketoamides was developed in the presence of PIDA and NaOH. This reaction proceeded at 25 °C in the absence of a metal catalyst to provide 2-hydroxy-3,3-dimethoxy-N-substituted butanamides in good to excellent yields from readily available starting materials. The application of this chemistry to the construction of α-hydroxy-β-ketoamides and quinolinones was also described.