Oxygen chemistry plays a pivotal role in numerous chemical, energy and environmental systems. Particularly, selective cleavage of C–H bonds by metal oxo species is highly desirable in the catalytic dehydrogenation of light alkanes. However, high selectivity of alkene is usually hampered through consecutive oxygenation reactions in conventional oxidative dehydrogenation (ODH) scheme. Herein, we show that dual-functional Mo-V-O mixed oxides selectively convert propane to propylene via an alternative chemical looping oxidative dehydrogenation (CL-ODH) approach. At 500 °C, we obtain 89% propylene selectivity at 36% pro-pane conversion over 100 dehydrogenation-regeneration cycles. We attribute such exceptional propylene yield—which far exceeds that of previously reported ODH catalysts—to the involvement and precise modulation of bulk lattice oxygen via atomic-scale doping of Mo, and show that increasing the binding energy of V-O bonds is critical to enhance the selectivity of propylene. This work provides the fundamen-tal understanding of metal-oxygen chemistry and a promising strategy for alkane dehydrogenation.