Abstract: To improve the aroma quality of cigarettes and to develop new glycoside flavors for cigarettes, a novel silver cluster was designed and synthesized for the catalytic synthesis of perillyl alcohol-β-D-glucoside. X-ray photoelectron spectroscopy(XPS)and electrospray ionization time-of-flight mass spectrometry(ESI-TOF-MS)were used to characterize the structure of the silver cluster. Perillyl alcohol-β-D-glucoside was synthesized by the novel silver cluster synthesis method, and its thermal stability and pyrolysis behavior were analyzed by thermogravimetric analysis(TG-DTG)and pyrolysis gas chromatography-mass spectrometry(Py-GC-MS). The results showed that: 1)The silver cluster consisted of an Au₉Ag₄ metal core composed of four silver atoms and nine gold atoms and a cluster periphery composed of four 1, 3-bis(diphenylphosphino)propane and four chlorine atoms. 2) Perillyl alcohol-β-D-glucoside was efficiently synthesized by the silver cluster method, and its yield was higher than that of the Koenigs-Knorr and phase-transfer catalytic methods. 3)The aroma release stability of perillyl alcohol-β-D-glucoside was significantly improved compared with that of perillyl alcohol when added to cigarettes. 4)Perillyl alcohol-β-D-glucoside underwent extensive pyrolysis when the temperature was above 300 ℃, the main pyrolysis product was perillyl alcohol, and a variety of other aroma components. To summarize, perillyl alcohol-β-D-glucoside was efficiently synthesized and was shown to effectively stabilize aroma release by decreasing volatilization of perillyl alcohol.