The mechanism of the reaction of CO 2 with H 2 on copper and nickel catalysts was studied by means of isotope, non-steady-state, and steady-state methods. Staged schemes of the process were proposed. The slow step of CO formation on the test catalysts is the reaction of the adsorbed carboxylate complex with a hydrogen atom. It was shown that hydrogen adsorption on the copper catalyst is dissociative in character. A formyl complex and hydrogen are involved in the slow step of methane formation on the nickel catalyst. It was found that the methane formation proceeds via a consecutive scheme through CO.