Several　hexagonal　layered　Mn/Co　oxide　catalysts　were　synthesized　from　Mn/Co-based　metal–organic　framework　(MOF)　precursors.　The　molar　ratio　of　Mn/Co　affects　the　physicochemical　properties　of　catalysts,　further　affects　their　catalytic　performance.　The　Mn/CoOx-3/2　sample　with　wide　interlayer　spacing　exhibited　the　highest　catalytic　activity　for　total　oxidation　of　propane,　with　a　T90　of　270　°C　at　120　L　g−1　h−1.　Low-temperature　reducibility,　oxygen　mobility,　water　vapor　tolerance,　and　oxygen　defects　play　the　key　roles　for　improving　catalytic　activity.　Oxygen　defects　were　calculated　using　the　density　functional　theory　(DFT).　The　results　show　that　the　doping　of　Mn　on　Co　oxide　is　conducive　to　the　formation　of　oxygen　vacancies.　Therefore,　benefiting　from　the　layered　structure　and　metal-doping　for　the　catalysts,　the　formation　of　more　abundant　interfacial　defects　can　further　improve　the　catalytic　performance.　This　study　offers　a　simple　way　to　synthesize　regular　layered　multi-metal　oxide,　which　can　expose　abundant　interface　defects　and　active　sites.　©　2023　Elsevier　B.V.