Oxidative　dehydrogenation　of　propane　(ODHP)　is　a　promising　route　for　propylene　production,　but　achieving　high　selectivity　towards　propylene　while　minimizing　COx　byproducts　remains　a　significant　challenge　for　conventional　metal　oxide　catalysts.　Here　we　propose　a　solution　to　this　challenge　by　employing　atomically　dispersed　dual-atom　catalysts　(M1M＇1-TiO2　DACs).　Ni1Fe1-TiO2　DACs　exhibit　an　ultralow　COx　selectivity　of　5.2%　at　a　high　propane　conversion　of　46.1%　and　520　degrees　C,　with　stable　performance　for　over　1000　hours.　Mechanistic　investigations　reveal　that　these　catalysts　operate　via　a　cooperative　Langmuir-Hinshelwood　mechanism,　distinct　from　the　Mars-van　Krevelen　mechanism　typical　of　metal　oxides.　This　cooperative　pathway　facilitates　efficient　conversion　of　propane　and　oxygen　into　propylene　at　the　dual-atom　interface.　The　superior　selectivity　arises　from　facile　olefin　desorption　from　the　dual-atom　sites　and　suppressed　formation　of　electrophilic　oxygen　species,　which　are　preferentially　adsorbed　on　Fe1　sites　rather　than　oxygen　vacancies.　This　work　highlights　the　potential　of　dual-atom　catalysts　for　highly　selective　ODHP　and　provides　insights　into　their　unique　catalytic　mechanism.