Treatment of alkylbenzenes with (diacetoxyiodo) benzene in the presence of catalytic amounts of p-toluenesulfonamide or p-nitrobenzenesulfonamide, and molecular iodine in 1, 2-dichloroethane at 60° C gave the corresponding (α-acetoxy) alkylbenzenes in good to moderate yields. The present reaction is a simple method for the introduction of an acetoxy group to the benzylic position of alkylbenzenes.