In order to develop a new resource of tobacco flavors, polyol esters of lower fatty-acid were synthesized. The polyols and C₂-C₆ acids used were well-applied tobacco flavorants, including acetic acid, butyric acid, isobutyric acid, isovaleric acid, hexylic acid, glycerol, xylitol and glucose. The objective of this research was to synthesize flavor precursors and also evaluate their functions. A novel catalyst, TiSiW₁₂O₄₀/TiO₂. was used in this research. The products were analyzed by MS, GC/MS and Py/GC/MS. The results of MS and GC/MS show that the products were mixed esters with single-, double-, triple- and total substituents and their iserners. The results of Py/GC/MS show that the corresponding lower fatty acid were released at 400°C and 800°C, which is the same as we assumed. Meanwhile, several other flavor compounds from polyol part are formed too. Sensory evaluation indicates glucose acetate, glucose isobutyrate, glucose isopentyrate, xylitol isopentyrate and xylitol caproate can provide satisfying tobacco flavoring effect, described as mild, smooth, harmonious, fresh, and wealthy. Their proper addition amounts are 10ppm, 20ppm, 20ppm, 5ppm, 5ppm respectively. The advantage of this kind of ester flavors is that they are non-volatile, without odor itself, stable storage, but they can release volatile small molecule flavor compounds as smoking.