Engineering　the　lattice　oxygen　reactivity　and　activation　of　gaseous　O2is　vital　for　boosting　methane　combustion　over　Co3O4.　Herein,　zinc　was　inserted　into　the　Co3O4matrix,　driven　by　its　slightly　larger　cationic　radius　and　lower　electronegativity　than　those　of　cobalt.　The　suitable　doping　of　zinc　offered　the　optimum　occupation　of　Zn2+at　the　tetrahedral　sites,　granting　more　active　Co3+sites.　The　formation　of　Co-Zn-O　solid　solution　delivered　the　lattice　disorder　and　endowed　cobalt　with　richer　electrons,　which　increased　the　oxygen　vacancy　density,　oxygen　storage　capacity,　migration　property　of　surface　lattice　oxygen,　and　reducibility　of　catalysts,　and　tuned　the　surface　acid-base　properties.　Also,　the　ability　to　adsorb　and　activate　aerial　O2of　catalysts　was　enhanced,　which　could　realize　more　effective　spillover　of　O2to　regenerate　lattice　oxygen.　These　entire　properties　allowed　the　redox　cycles　to　proceed　more　smoothly　on　the　Co3+-O　pair　sites　for　Zn0.6Co2.4O4compared　to　its　analogues.　Consequently,　Zn0.6Co2.4O4manifested　more　effective　methane　combustion　with　its　T90at　380　°C　while　holding　outstanding　long-term　stability.　©　2022　American　Chemical　Society.　All　rights　reserved.