Zeolites-supported Cu-based catalysts for the vapor-phase synthesis of 3-methylindole from glycerol and aniline were investigated. The catalysts were characterized by N-2 adsorption, XRD, NH3-TPD and TG-DTA techniques. The results indicated that Cu/NaY catalyst exhibited higher activity and selectivity than Cu/5A, Cu/HZSM-5 or Cu/MCM-41 due to better dispersion of copper particles and larger amount of weak acid sites on the catalyst. The addition of Na2O to Cu/NaY not only improved the selectivity of the catalyst efficiently, but also inhibited the deactivation of the catalyst. Over Cu/NaY-Na2O, the selectivity of 3-methylindole reached 72.3% and the yield of the aim product was up to 50.4%. The characterizations revealed that Na2O promoter could decrease the amount of middle-strong acid sites of the catalyst remarkably as well as prevent from the formation of the coke. Furthermore, a probable catalytic mechanism for the synthesis of 3-methylindole from glycerol and aniline was proposed. (c) 2013 Elsevier B.V. All rights reserved.