Converting CO₂ to methane via catalytic routes is an effective way to control the CO₂ content released in the atmosphere while producing value-added fuels and chemicals. In this study, the CO₂ methanation performance of highly dispersed Ni-based catalysts derived from aqueous miscible organic layered double hydroxides (AMO-LDHs) was investigated. The activity of the catalyst was found to be largely influenced by the chemical composition of Ni metal precursor and loading. A Ni-based catalyst derived from AMO-Ni₃Al₁-CO₃ LDH exhibited a maximum CO₂ conversion of 87.9% and 100% CH₄ selectivity ascribed to both the lamellar catalyst structure and the high Ni metal dispersion achieved. Moreover, due to the strong Ni metal–support interactions and abundant oxygen vacancy concentration developed, this catalyst also showed excellent resistance to carbon deposition and metal sintering. In particular, high stability was observed after 19 h in CO₂/H₂ reaction at 360 °C.