A photoinduced copper-mediated acyloxylation of arylthianthrenium or arylphenoxathiinium salts with either aliphatic or aromatic carboxylic acids is described for the convenient synthesis of O-aryl esters. The reaction has shown obvious advantages, such as high efficiency, good functional group tolerance, excellent chemoselectivity, and capacity for esterification of complex drug molecules, offering a practical synthetic route to multifunctionalized and sterically congested O-aryl esters, which are potentially useful in the development of new prodrugs or twin drugs.