The influence of the pore structures of zeolites on their selectivities for the formation of ethylene and propylene was examined in the conversion of 2-methyl-2-butene and 2-pentene over a wide range of pentene conversion. The selectivities for ethylene and propylene were highly dependent on both the spatial volume of the zeolite cavity and the dimensionality of the pore structure. Only when the specific spatial volume of zeolite, with one- or two-dimensional pore structure, was almost the same as the volume of pentyl cations did the selective production of both ethylene and propylene proceed via the monomolecular cracking of pentene. When the spatial volume of the zeolite cavity was enough larger than the volume of pentyl carbenium ions, the reaction of pentyl carbenium ions with pentene could proceed to produce decyl carbenium ions, and by following their beta-scission, butenes and hexenes were preferentially formed, together with ethylene and propylene. (C) 2013 Elsevier Inc. All rights reserved.