Co3O4　spinel　has　been　widely　investigated　as　a　promising　catalyst　for　the　oxidation　of　volatile　organic　compounds　(VOCs).　However,　the　roles　of　tetrahedrally　coordinated　Co2+　sites　(Co2+Td)　and　octahedrally　coordinated　Co3+　sites　(Co3+Oh)　still　remain　elusive,　because　their　oxidation　states　are　strongly　influenced　by　the　local　geometric　and　electronic　structures　of　the　cobalt　ion.　In　this　work,　we　separately　studied　the　geometrical-site-dependent　catalytic　activity　of　Co2+　and　Co3+　in　VOC　oxidation　on　the　basis　of　a　metal　ion　substitution　strategy,　by　substituting　Co2+　and　Co3+　with　inactive　or　low-active　Zn2+(d0),　Al3+(d0),　and　Fe3+(d5),　respectively.　Raman　spectroscopy,　X-ray　absorption　fine　structure　(XAFS),　and　in　situ　DRIFTS　spectra　were　thoroughly　applied　to　elucidate　the　active　sites　of　a　Co-based　spinel　catalyst.　The　results　demonstrate　that　octahedrally　coordinated　Co2+　sites　(Co2+Oh)　are　more　easily　oxidized　to　Co3+　species　in　comparison　to　Co2+Td,　and　Co3+　are　responsible　for　the　oxidative　breakage　of　the　benzene　rings　to　generate　the　carboxylate　intermediate　species.　CoO　with　Co2+Oh　and　ZnCo2O4　with　Co3+Oh　species　have　demonstrated　good　catalytic　activity　and　high　TOFCo　values　at　low　temperature.　Benzene　conversions　for　CoO　and　ZnCo2O4　are　greater　than　50%　at　196　and　212　°C,　respectively.　However,　CoAl2O4　with　Co2+Td　sites　shows　poor　catalytic　activity　and　a　low　TOFCo　value.　In　addition,　ZnCo2O4　exhibits　good　durability　at　500　°C　and　strong　H2O　resistance　ability.　©　2017　American　Chemical　Society.