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Herein, we investigated the α-acetoxylation of ketones through various experiments. These include screening of reaction conditions, analysis of reactivity and selectivity over diverse ketones, kinetic study of the reaction of monoacetoxylation and diacetoxylation, density functional theory calculations for estimating the energy and structure, and analysis of natural bond orbitals. Based on the reaction products of the study, the pseudo first-order model is determined as the best model for the reaction, and the identification of the reaction intermediates indicates that iodonium is an essential intermediate in the reaction. Additionally, kinetic studies and theoretical calculations reveal that the reaction may utilize a different mechanism depending on the ketone structure; in this case, however, we focused on the α-acetoxylation of 4-tert-butylcyclohexanone. Based on these findings, we propose a reaction mechanism and the corresponding behavior description for iodine(III) in α-acetoxylation reactions. [ABSTRACT FROM AUTHOR]