Perovskite-type catalysts group one Ln(0.6)Sr(0.4)Fe(x)Co(1-x)O(3) (Ln = Nd, Pr, Gd, Sm, La, 0 < x < 1), (La0.8Sr0.2)(0.9)MnO3 and La0.8Sr0.2CrO3, and group two sodium-doped ACoO(3) (Na:A = 1:4) and A(0.8)Na(0.2)MnO(3) (A = La, Gd, Sm) were synthesized, and their properties for activation of methane were evaluated in a quartz reactor first. Catalysts group one presented much higher activity than catalysts group two at temperatures below 740 degrees C, and the main product was, however, carbon dioxide. Group two showed much higher selectivity to C-2 hydrocarbons than group one. Electrochemical measurements were conducted in a solid oxide membrane reactor with sodium-doped LaCoO3 as the catalyst electrode. It was found that electrochemical supply of O2- to the catalyst film can significantly change the rate of methane consumption and C-2 hydrocarbon selectivity. The total selectivity to C-2 hydrocarbon exceeded 80% in the case of the electrochemical supply of oxygen. On the basis of the experimental results, a kinetic model was suggested to describe the reaction results.