Enantioselective Cu-catalyzed acyloxylations of six-membered cyclic non-coordinating diaryliodonium salts with carboxylic acids were present. The reaction displays a wide substrate scope and broad functional group tolerance under mild reactions. Control experiments demonstrated that the reaction worked with diaryliodonium salts prior to anion exchangement, and steric interaction between the substrate and Cu catalysis determined the stereoinduction. Late-stage functionalization and further synthetic transformation produced structurally diverse multi-ortho-substituted triarylmethane scaffolds that are hardly accessed with other synthetic approaches.