Preparation of triacetyl ribose α isomers. The specific method uses 5-deoxy-D-ribose as starting material, which is acetylated in the presence of acrylate acetate/ferric chloride to obtain a mixture of triacetyl ribose isomers, which is further purified to the triacetyl ribose α isomer pure product. The reaction raw material 5-deoxy-D-ribose is a known compound, and samples thereof can be obtained by the synthetic method of Patent WO2008/105593, in which samples were prepared by heating and hydrolyzing with sulfuric acid from methyl-5-deoxy-2,3-O-isopropylidene-β-D-riboside (V).