Metal　oxide　catalysts　with　surface　oxygen　vacancies　show　promise　for　photo-thermal　catalytic　VOC　destruction,　yet　the　role　of　vacancy　quantity　in　VOC　degradation　remains　underexplored.　Here,　three-dimensionally　ordered　macroporous　(3DOM)　LaMn1.2O3　annealed　at　350　°C　(LMO-350　°C)　exhibited　outstanding　toluene　oxidation,　achieving　100　%　conversion　and　92　%　mineralization　at　WHSV　of　35,　000　mL　g−1　h−1　under　focused　solar　irradiation　with　excellent　stability.　Moderate　surface　oxygen　vacancies　were　found　to　enhanced　charge　carrier　migration,　reduced　activation　barriers,　and　promoted　toluene　adsorption　and　activation.　In　contrast,　excessive　vacancies　impaired　low-temperature　reducibility　and　oxygen　mobility,　reducing　effectiveness.　The　study　underscores　that　balancing　surface　oxygen　vacancies　in　LMO　proved　critical　for　maintaining　good　reducibility,　high　oxygen　mobility,　and　low　activation　energy,　ensuring　effective　mineralization.　Notably,　LMO-350　°C　also　degraded　acetone,　ethyl　acetate,　benzene,　o-xylene,　and　their　mixtures　under　ambient　solar　irradiation.　A　life-cycle　assessment　underscored　the　significance　of　solar　utilization,　highlighting　its　potential　to　improve　economic　and　ecological　sustainability　in　photo-thermal　catalytic　technologies　for　environmental　remediation.　©　2025　Elsevier　B.V.