In this study, CoAlx-LDH hydrotalcite-like was used as the precursors to prepare the CoAlx-LD composite catalysts for the DRM reaction. The transition metal Co was the main catalytic active centers for the DRM reaction. The layered structure of the hydrotalcite-like CoAlx-LDH precursors promoted the highly dispersed Co0 active centers to be formed in the CoAlx-LD catalysts. In addition, synergistic effects between active sites, basic sites and oxygen vacancies can promote the DRM catalytic performances of CoAl composite catalysts. Meanwhile, the Co/Al mole ratio can regulate the active sites, basic sites and oxygen vacancies in the catalysts, thereby affecting its catalytic performances. The CoAl12-LD catalyst with a Co/Al mole ratio of 1/2 exhibited excellent DRM catalytic performances. The CH4 and CO2 conversions on the prepared CoAl12-LD catalyst achieved 86.8% and 53.4% at atmospheric pressure and 700 °C, respectively. In addition, the catalyst also showed excellent use stability in the DRM reaction.