The　high-efficient　catalyst　is　critical　for　volatile　organic　compounds　(VOCs)　catalytic　oxidation.　MnO2　nanoparticles　encapsuled　in　spheres　of　Ce-Mn　solid　solution　(package　structure)　are　controllable　designed　and　applied　for　the　catalytic　oxidation　of　toluene,　a　representative　of　VOCs.　Our　study　indicates　that　the　obtained　Ce1M2　(molar　ratio　of　Ce:Mn　=　1:2)　catalyst　displays　much　better　toluene　oxidation　activity　than　pristine　MnO2　and　CeO2.　Meanwhile,　the　shell　of　Ce-Mn　solid　solution　contributes　to　superior　thermal　stability　and　resistance　against　5　vol%　H2O.　The　synergistic　effect　between　two　oxides　is　maximized　by　the　package　structure,　giving　rise　to　high　BET　surface　area,　good　reducibility　and　fast　oxygen　mobility,　which　in　turn　leads　to　the　outstanding　catalytic　performance　in　Ce1Mn2.　Additionally,　in　situ　DRIFTS　results　indicate　that　intermediate　species　-COO　and　-O-CH(=O)　are　found　during　the　catalytic　oxidation　of　toluene　over　Ce1Mn2,　which　is　mainly　dominated　by　MvK　mechanism.