A copper catalyzed direct α-oxyacylation of ketones with carboxylic acids has been developed. Various acids including aromatic and aliphatic acids are well tolerated, and the scope of ketones is also investigated. This protocol provides a convenient and benign method for the synthesis of α-acyloxycarbonyl compounds by using oxygen as the oxidant. In addition, we have investigated the role of copper and trapped the key intermediate to confirm the mechanism.