In order to develop new tobacco flavors, eight polyol esters were synthesized from polyols and lower fatty acids with TiSiW12O40/TiO2 as a catalyst. The synthesizers were analyzed by MS, GC/MS and Py/GC/MS, and their performance as cigarette flavorings were evaluated. The results showed that: 1) TiSiW12O40/TiO2 could effectively catalyze the synthesis of the esters, and the products were a mixture of esters of single to five acyloxyes; 2) corresponding lower fatty acids and a variety of volatile aroma compounds of minor molecule were generated when the products were pyrolyzed; 3) the synthesized glucose acetate, glucose isobutyrate, glucose isopentyrate, xylitol isopentyrate and xylitol caproate could harmonize the smoke flavor, improve flavor quality and taste of Virginia type cigarettes, their preferable applying rates were 10, 20, 20, 5, 5 µg per gram of cut tobacco, respectively; 4) the flavoring effects of glycerol butyrate, xylitol butyrate and xylitol isobutyrate were not remarkable, moreover, they will impart negative influences to sensory quality of cigarette if their addition rate is too high.