Oxidative dehydrogenation (ODH) of propane to propylene offers a promising large-scale alternative to direct dehydrogenation. The reported metal oxides catalysts generally cause over-oxidation of propylene to COx, thus hindering the commercialization of ODH processes. In this study, a layered borosilicate zeolite was demonstrated as highly active and selective catalyst for the oxidative dehydrogenation of propane, showing a propylene selectivity of 83.6% and the total light olefins (propylene and ethylene) selectivity of 91.2% at a propane conversion of 3.9%. Further, at a propane conversion of 15.6%, the catalyst exhibited a propylene selectivity of 80.4% and the total light olefins selectivity of 91.6% at 530 degrees C. Structural characterization revealed that the abundance of defective trigonal boron species (13[3](a) and B[3](b)) was responsible for the activity of propane ODH. (C) 2020 Elsevier Inc. All rights reserved.