The　eco-friendly　features　and　desirable　catalytic　activities　of　Fe-based　catalysts　make　them　highly　promising　for　propane　dehydrogenation　(PDH).　However,　simultaneously　improving　their　stability　and　activity　remains　a　challenge.　Here,　we　present　a　strategy　to　address　these　issues　synergistically　by　anchoring　single-atom　Fe−Cl　sites　in　Al3+　vacancies　of　Al2O3.　The　as-synthesized　Fe−Cl/Al2O3　catalyst　exhibited　greater　charge　transfer　between　Cl　and　Fe　than　that　between　O　and　Fe　in　conventionally　impregnated　single-atom　Fe/Al2O3　catalysts,　resulting　in　higher　effective　magnetic　moments　for　Fe−Cl/Al2O3　compared　to　Fe/Al2O3.　When　tested　in　PDH,　the　durability　of　Fe−Cl/Al2O3　exceptionally　lasted　for　250　h　under　continuous　regeneration　conditions　comprising　60　%　C3H8　(40　%　N2),　followed　by　pure　C3H8　at　600　°C　while　maintaining　a　high　propylene　space-time　yield　of　1.2　molC3H6　gFe−1　h−1,　surpassing　the　performance　of　previously　developed　Fe-based　PDH　catalysts.　We　demonstrate　that　anchoring　Fe−Cl　into　Al3+　vacancies　simultaneously　enhances　stability　and　suppresses　coke　formation,　owing　to　unique　atomically　dispersed　Fe−Cl　active　structures.　Compared　with　Fe/Al2O3　catalysts,　charge　transfer　between　Cl　and　Fe　active　centers　reduces　the　activation　energy　barrier　for　C−H　activation　during　C3H8　dehydrogenation,　thereby　improving　catalytic　activity;　this　may　be　related　to　their　spin　state　as　observed　in　in-situ　X-ray　emission　spectroscopy　studies　during　PDH.　©　2025　Wiley-VCH　GmbH.