AbstractMetal oxide‐based catalysts are widely studied in oxidative propane dehydrogenation (OPDH), but they usually suffered from the low olefin activity, which is believed to be related to the active centers of metal‐oxygen species. Herein, we report an effective cation‐exchange strategy towards the development of TiO2 nanosheets embedded isolated Fe species (Fe1TiO2) as a highly‐active and stable catalyst for OPDH. It exhibits an olefin yield of 38.2% at 520°C, 10.9 and 2.4 times higher than that of pure TiO2 (3.5%) and Fe2O3 (15.6%), respectively; and it shows a superior 100‐h durability. The isolated Fe species embedded in Fe1TiO2 are demonstrated to serve as active centers. Multiple characterizations including in situ Fourier transform infrared spectroscopy (FT‐IR) and theoretical calculations demonstrate that the isolated Fe species in Fe1TiO2 are favorable for the generation of olefins, which produce propylene (C3) through an appropriate FeH dehydrogenation pathway with a low energy barrier.