The CoCex composite catalysts prepared by hydrothermal assisted template agent CTAB, have superior catalytic performances for CH₄/CO₂ dry reforming (DRM). The physicochemical properties of the catalysts were investigated in depth with the help of XRD, H₂-TPR, CO₂-TPD, ICP, Quasi in-situ XPS and N₂ adsorption–desorption measurements. The transition metal Co is the main active center in the DRM reaction, which can easily release the outer electrons in the reaction to activate the reactant molecules. The introduction of Ce species can promote the highly dispersed metal Co species and catalytic active centers to be formed, as well as the adsorption and activation of CO₂ molecules by the catalyst. Ce species can produce strong electronic effects with Co species, which can promote the electron-deficient CeO_2-δ and electron-rich Co^δ- species to be formed. The formation of CeO_2-δ species facilitates the adsorption and activation of CO₂ molecules, and the active oxygen species on the CeO_2-δ surface facilitates the oxidative activation for CH₄ molecules. The CH₄ and CO₂ reactant molecules can be adsorbed and activated by the formed Co^δ- species to form CH_4-x (x = 0–4) and CO₂^δ- reactive species, which can promote the DRM reaction. The Co/Ce molar ratio has an important effect on the physicochemical properties and CO₂ adsorption performance of CoCex catalysts. And the CoCe2 catalyst prepared at a 2.0 Co/Ce molar ratio exhibited superior catalytic performance and high stability for the DRM reaction. The CH₄ and CO₂ conversion of the CoCe2 catalyst reached 88.6%, and 52.1% at 700 °C, respectively. In addition, the CoCe2 catalyst can maintain high cycle stability for CH₄/CO₂ dry reforming.