An　innovative　simplified　modification　method　for　red　mud　had　been　proposed,　which　enabled　its　utilization　as　an　active　Fe2O3-rich　component　for　catalytic　oxidation　of　toluene.　The　Box-Behnken　design,　based　on　Response　Surface　Methodology　(RSM),　was　employed　to　optimize　the　modification　of　bauxite　residue　using　oxalic　acid　combined　with　UV　irradiation.　Based　on　the　experimental　conditions,　the　optimal　conditions　for　three　independent　parameters　were　determined:　acid　leaching　time　(2　hours),　UV　irradiation　time　(1　hour),　and　acid　dosage　(150　ml),which　was　in　order　to　enhance　the　maximum　catalytic　efficiency　of　toluene　at　300　°C.　Under　the　optimal　preparation　conditions　provided　by　the　Box-Behnken　design,　the　catalytic　efficiency　of　toluene　at　300°C　could　reach　99.2%.　In　comparison　to　the　acid-modified　mud　(MRM)　and　untreated　bauxite　residue　(RM),　the　aluminum　refinery　residue　modified　with　oxalic　acid-assisted　UV　irradiation　(MRM-UV)　exhibited　the　formation　of　oxalate　sub-iron　precipitates,　resulting　in　significantly　lower　catalytic　temperatures　(238°C).　Furthermore,　through　XRF,　XRD,　XPS,　O2-TPD,　and　H2-TPD　analysis,　it　was　discovered　that　a　large　amount　of　iron　oxide　and　calcium　oxide　formed　CaO+Fe2O3→Ca2Fe2O5,　strengthening　the　interaction　between　iron　and　calcium,　augmenting　the　migration　rate　of　lattice　oxygen　from　the　bulk　phase　to　the　surface.　Consequently,　T50　were　reduced　by　20.9%　and　31.8%　when　compared　to　MRM　and　RM.　Moreover,　the　CO2　selectivity　of　MRM-UV　increased　from　8.6%　to　70.5%　compared　to　RM　at　300°C.　Using　in　situ　DRIFTS,　the　reaction　pathway　of　toluene　on　MRM-UV　was　identified　as　benzyl　alcohol　→　benzaldehyde　or　benzoyl　→　benzoate→maleic　anhydride→CO2　and　H2O.　The　process　refinement　reduced　VOCs　emissions　and　promoted　sustainable　waste　management　by　combining　oxalic　acid　with　catalytically　active　red　mud.　©　2024　Elsevier　B.V.