A chelation-assistedpalladium-catalyzed acyloxylation of the sp3 C–H bond of benzyl by carboxylic acid is described, which employs PhI(OAc)2 as a stoichiometric oxidant. The procedure tolerates a series of functional groups, such as methoxyl, chloro, bromo, iodo, vinyl, formyl, phenolic hydroxyl, nitro, and cyano groups, providing the acyloxylation products in moderate to good yields.