Glycerol can be obtained as a by-product during biodiesel manufacture. It is important to convert glycerol to value-added products. Glycerol esterification with acetic acid is one of the most promising approaches for glycerol utilization. It is usually difficult to obtain diacetin with good activity and selectivity. In this work, glycerol esterification with acetic acid over different metal oxides, such as Bi2O3, Sb2O3, Sn O2, Ti O2, Nb2O5 and Sb2O5, was investigated. It was found that in the six investigated metal oxides, only Sb2O5 resulted in good activity and selectivity to diacetin. Under the optimized conditions, the glycerol conversion reached 96.8%,and the selectivity to diacetin reached 54.2%, while the selectivity to monoacetin and triacetin was 33.2% and12.6%, respectively. The catalysts were characterized with FT-IR spectra of adsorbed pyridine, which indicated that in the six investigated metal oxides, only Sb2O5 possessed Br?nsted acid sites strong enough to protonate adsorbed pyridine. The good catalytic activity and selectivity to diacetin might be mainly attributable to the Br?nsted acid sites of Sb2O5. Reusability tests showed that with Sb2O5 as catalyst, after six reaction cycles, no significant change in the glycerol conversion and the selectivity to diacetin was observed. Glycerol can be obtained as a by-product during biodiesel manufacture. It is important to convert glycerol to value-added products. Glycerol esterification with acetic acid is one of the most promising approaches for glycerol utilization. It is usually difficult difficult to obtain diacetin with good activity and selectivity. It was found that in the six investigated metal oxides, only Sb 2 O 5, was investigated resulted in good activity and selectivity to diacetin. Under the optimized conditions, the glycerol conversion reached 96.8%, and the selectivity to diacetin reached 54.2%, while the selectivity to monoacetin and triacetin was 33.2% and 12.6% respectively. characterized with FT-IR spectra of adsorbed pyridine, which indicated that in the six investigated metal oxides, only Sb2O5 possessed Br? nsted acid sites strong enough to protonate ads orbed pyridine. The good catalytic activity and selectivity to diacetin might be mainly attributable to the Br? nsted acid sites of Sb2O5. Reusability tests showed that with Sb2O5 as catalyst, after six reaction cycles, no significant change in the glycerol conversion and the selectivity to diacetin was observed.