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Selective oxidation of α-hydroxy esters is one of the most important methods to prepare high value-added α-keto esters. An efficient catalytic system consisting of Zn(NO₃)₂/VOC₂O₄ is reported for catalytic oxidation of α-hydroxy esters with molecular oxygen. Up to 99% conversion of methyl DL-mandelate or methyl lactate could be facilely obtained with high selectivity for its corresponding α-keto ester under mild reaction conditions. Zn(NO₃)₂ exhibited higher catalytic activity in combination with VOC₂O₄ compared with Fe(NO₃)₃ and different nitric oxidative gases were detected by situ attenuated total reflection infrared (ATR-IR) spectroscopy. UV-vis and ATR-IR results indicated that coordination complex formed in Zn(NO₃)₂ in CH₃CN solution was quite different from Fe(NO₃)₃; it is proposed that the charge-transfer from Zn²⁺ to coordinated nitrate groups might account for the generation of different nitric oxidative gases. The XPS result indicate that nitric oxidative gas derived from the interaction of Zn(NO₃)₂ with VOC₂O₄ could be in favor of oxidizing VOC₂O₄ to generate active vanadium (V) species. It might account for different catalytic activity of Zn(NO₃)₂ or Fe(NO₃)₃ combined with VOC₂O₄. This work contributes to further development of efficient aerobic oxidation under mild reaction conditions.