The invention provides a catalyst for carbon dioxide plasma decomposition and a preparation method thereof. The catalyst is prepared from a spherical carrier and a non-noble metal oxide loaded on thespherical carrier, wherein the spherical carrier contains one or more of aluminum oxide, titanium oxide, 13X molecular sieve and silicon oxide; the mass of the non-noble metal oxide is 1 to 40 percentof the mass of the spherical carrier. The invention further provides a catalytic system of carbon dioxide plasma decomposition and application thereof. The system is filled with the catalyst providedby the invention, and the catalyst adapts to plasma, thereby effectively reducing the activation energy barrier of the plasma, and increasing the energy efficiency in a carbon dioxide plasma decomposition process. The result of the embodiment shows that the conversion rate of carbon dioxide is up to 25 percent and the energy efficiency is up to 25 percent when the catalyst provided by the invention is applied to a carbon dioxide plasma decomposition system.