Several types of microporous molecular sieves with similar n(Si)/n(Al) ratios (except for SAPO-34) and different pore structures were prepared and applied as ethene-to-propene (ETP) catalysts. H-SSZ-13 zeolite consisting of chabazite cages connected via 8-ring windows possessed the highest adsorption capacity for ethene and exhibited the best activity in the ETP conversion. The decreasing amount of Brensted acid sites after dealumination of H-SSZ-13 caused a prolonged lifetime of the catalyst in the ETP reaction. The reaction mechanism and deactivation behavior of H-SSZ-13 catalysts during the ETP process were investigated by in situ FT-IR, UV/Vis, GC-MS, TGA and H-1 MAS NMR methods. Ethene was rapidly oligomerized and converted into naphthalene-based carbenium ions, playing a significant role in the ETP reaction. The accumulation of these species lead to the formation of polycyclic aromatics, which are responsible for a total blocking of H-SSZ-13 pores, and cause the deactivation of the catalyst. (c) 2014 Elsevier Inc. All rights reserved.