Developing　facile　preparation　method　to　obtain　the　satisfied　low-temperature　catalytic　performance　of　transitional　metal　oxide-based　materials　is　still　a　challenge　in　deep　degradation　of　VOCs.　Here,　a　series　of　Mn-Cu　bimetallic　oxide　catalysts　were　prepared　by　one-step　hydrothermal-redox　method　for　catalytic　total　oxidation　of　toluene.　The　CH3COOH　concentration,　Cu/Mn　molar　ratio　and　calcination　temperature　greatly　affected　the　crystal　structure,　micromorphology　and　catalytic　performance.　Amongst,　MnCu　spinel　structured　catalyst　exhibited　excellent　low-temperature　catalytic　activity,　superior　durability　and　water　resistance　in　toluene　total　oxidation　owing　to　its　abundant　surface　adsorbed　oxygen　species,　higher　amount　of　Cu+　and　Mn3+　and　excellent　low-temperature　reducibility.　The　reaction　rate　of　MnCu　was　7.0　times　higher　than　that　of　MnCu0.5　at　210　°C.　The　cyclic　redox　process　with　enough　oxygen　vacancy　played　a　vital　role　in　toluene　oxidation.　The　deep　oxidation　of　benzene　was　the　key　step　in　the　toluene　oxidation.　Proton　transfer　reaction-mass　spectrometry　(PTR-MS)　results　revealed　the　reaction　intermediates　including　benzaldehyde,　benzene　and　phenol,　which　further　decomposed　to　acetone,　ethanol,　acetic　acid,　ketone　and　acetaldehyde　by　ring　opening　before　total　mineralization.　Therefore,　PTR-MS　provided　a　facile　method　to　investigate　the　reaction　mechanism　of　toluene　oxidation.　©　2021　Elsevier　B.V.