Different　crystallographic　structures　of　Mn　oxides　usually　lead　to　diverse　coordination　geometries　and　oxidation　states　of　MnO　6　,　which　in　turn　show　strikingly　different　catalytic　activities.　In　this　study,　methane　oxidation　performances　over　Mn　oxides　with　various　crystalline　structures　were　investigated,　including　α-MnO　2　(double　chains　of　Mn　4+　O　6　octahedra),　α-Mn　2　O　3　(symmetry-inequivalent　Mn　3+　O　6　),　two-dimensional　mesoporous　β-MnO　2　(labels　as　Meso-MnO　2　,　single　chains　of　Mn　4+　O　6　octahedra)　and　one-dimensional　β-MnO　2　(single　chains　of　Mn　3+/4+　O　6　octahedra).　The　results　demonstrate　that　the　methane　oxidation　activities　are　dependent　on　their　crystallographic　structures,　and　follow　an　order　of　α-MnO　2　>　β-MnO　2　>　α-Mn　2　O　3　>　Meso-MnO　2　.　Meanwhile,　α-MnO　2　exhibits　good　durability　and　excellent　9.5vol%H　2　O/10vol%CO　2　resistance　ability.　EXAFS,　Raman,　XPS,　O　2　-TPD-MS　and　CH　4　-TPR-MS　studies　indicate　that　the　outstanding　catalytic　activity　over　α-MnO　2　is　due　to　higher　surface　Mn　concentration,　more　active　oxygen　species　and　mono-μ-oxo　bridged　corner-shared　[MnO　6　]　sites,　and　excellent　reducibility.　More　importantly,　a　new　insight　into　reaction　mechanism　of　methane　oxidation　over　Mn　oxides　was　proposed　at　the　molecular　level.　©　2018　Elsevier　B.V.