This work uncovered the regio/site-selective benzoylation of 1,2- and 1,3-diols and glycosides containing a cis-vicinal diol using a catalytic amount of FeCl3 with the assistance of acetylacetone. FeCl3 may initially form [Fe(acac)3] (acac = acetylacetonate) with excess acetylacetone in the presence of diisopropylethylamine (DIPEA) in acetonitrile at room temperature. Then, benzoylation was catalyzed by Fe(acac)3 with added benzoyl chloride in the presence of DIPEA under mild conditions as reported. This reaction produced selectivities and isolated yields similar to or slightly lower than the reaction using Fe(acac)3 as a catalyst in most cases. The result provides not only the green and convenient selective benzoylation method associated with the most inexpensive catalysts but also the possibility that the effects of various metal salts and ligands on the regioselective protection can be extensively investigated in future study to obtain the optimized catalytic system.