In the microwave and RF plasma catalytic reaction at room temperature, the decomposition of natural gas over Pd-NiO/γ-Al2O3 was carried out. The decomposition of methane is caused by collision by excitation of unstable electronic state. Measuring the flow rate and plasma power can represent kinetic data and mechanism. The conversion of C2 hydrocarbons was increased from 47% to 63.7% in the microwave plasma catalytic reaction within electric field. Comparing the activities of catalysts, Pd-NiO/γ-Al2O3 bimetallic catalyst was more active than Pt-Sn/γ-Al2O3 catalyst because of modifying the surface of catalysts by carbon formation. In RF plasma catalytic reaction, we obtained high C2 yield of 72%, in which the conversion and selectivity of C2 hydrocarbons were related to the applied power and feed rate of natural gas.