Direct propane dehydrogenation (PDH) to propylene is a desirable commercial reaction but is highly endothermic and severely limited by thermodynamic equilibrium. Routes that oxidatively remove hydrogen as water have safety and cost challenges. We coupled chemical looping-selective hydrogen (H2) combustion and PDH with multifunctional ferric vanadate-vanadium oxide (FeVO4-VOx) redox catalysts. Well-dispersed VOx supported on aluminum oxide (Al2O3) provides dehydrogenation sites, and adjacent nanoscale FeVO4 acts as an oxygen carrier for subsequent H2 combustion. We achieved an integral performance of 81.3% propylene selectivity at 42.7% propane conversion at 550°C for 200 chemical looping cycles for the reoxidization of FeVO4. Based on catalytic experiments, spectroscopic characterization, and theory calculations, we propose a hydrogen spillover-mediated coupling mechanism. The hydrogen species generated at the VOx sites migrated to adjacent FeVO4 for combustion, which shifted PDH toward propylene. This mechanism is favored by the proximity between the dehydrogenation and combustion sites.