As　an　industrial　solid　waste　produced　by　alumina　industry,　red　mud　was　modified　as　support　of　Pd　catalysts　for　toluene　catalytic　oxidation　in　this　paper.　The　xPd/MRM　catalysts　had　high　activity　for　toluene　catalytic　oxidation,　and　the　0.3Pd/MRM　catalyst　showed　the　best　catalytic　performance　(T　50　=　175　°C　and　T　100　=　200　°C).　The　results　indicated　that　the　prepared　0.3Pd/MRM　catalyst　had　more　ratio　of　surface-adsorbed　oxygen　and　Fe3+,　rather　than　MRM　and　RM,　which　benefitted　to　the　toluene　oxidation.　The　excessive　Pd　species　and　the　growth　of　the　PdO　nanoparticles　negatively　affected　the　catalytic　efficiency　of　toluene.　0.4Pd/MRM　activity　decreased　because　of　PdO　aggregation　in　the　catalyst,　which　could　be　confirmed　by　TEM　analysis.　The　results　of　XPS,　H2-TPR,　FT-IR,　O2-TPD,　and　Raman　examination　revealed　that　the　formation　of　Pd-O-Fe　under　the　interaction　between　Fe　in　MRM　and　Pd　(Pd2+　+　Fe　2+　→　Pd0　+　Fe3+)　increased　the　electron　transfer　and　raised　the　mobility　of　surface-adsorbed　oxygen.　Furthermore,　in　situ　DRIFTS　and　GC-MS　were　used　to　detect　intermediate　products　of　catalytic　reactions,　and　the　reaction　mechanism　of　catalysts　was　also　studied.　The　catalytic　oxidation　of　toluene　on　0.3Pd/MRM　catalyst　might　have　two　reaction　paths　simultaneously.　The　first　reaction　path　would　be　toluene　→　species　benzyl　→　benzaldehyde　→　benzoic　acid　→　long-chain　aldehydes　or　carboxylic　acids　→　CO2　and　H2O.　The　second　reaction　path　would　be　toluene　→　benzene　→　phenol　→　long-chain　aldehydes　or　carboxylic　acids　→　CO2　and　H2O.　©　2023,　The　Author(s),　under　exclusive　licence　to　Springer-Verlag　GmbH　Germany,　part　of　Springer　Nature.