Highly sensitive and stable gas sensors have attracted much attention because they are the key to innovations in the fields of environment, health, energy savings and security, etc. Sensing materials, which influence the practical sensing performance, are the crucial parts for gas sensors. Metal–organic frameworks (MOFs) are considered as alluring sensing materials for gas sensors because of the possession of high specific surface area, unique morphology, abundant metal sites, and functional linkers. Herein, four kinds of porous hierarchical Co3O4structures have been selectively controlled by optimizing the thermal decomposition (temperature, rate, and atmosphere) using ZIF-67 as precursor that was obtained from coprecipitation method with the co-assistance of cobalt salt and 2-methylimidazole in the solution of methanol. These hierarchical Co3O4 structures, with controllable cross-linked channels, meso-/micropores, and adjustable surface area, are efficient catalytic materials for gas sensing. Benefits from structural advantages, core–shell, and porous core–shell Co3O4exhibit enhanced sensing performance compared to those of porous popcorn and nanoparticle Co3O4 to acetone gas. These novel MOF-templated Co3O4 hierarchical structures are so fantastic that they can be expected to be efficient sensing materials for development of low-temperature operating gas sensors.