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Methane is the main component of natural gas, and a major greenhouse gas as well. The global warming potential of methane is 21 times higher than that of CO2. Therefore, it will be greatly contributing to energy conversion and greenhouse gas emission reduction to convert methane to high value-added chemical products, such as chlorinated methanes （CMS）. The chlorination of methane by pulsed electrical discharge in a wire- cylinder reactor was experimentally investigated. The conversion of CH4, yield and selectivity of chlorinated methanes （CMS） with different operation parameters were investigated. The reaction mechanism of methane chlorination was also studied.Experimental results showed that with the increase of energy intensity, the conversion of CH4 and the total yield and selectivity of CMS increased. The conversion of CH4 and selectivity of CMS was influenced by the distance between electrodes, electrode material, V（Cl2）/V（CH4） ratio and residence time. The addition of inert gas can improve the conversion of CH4 and the yield of CH2Cl2 and CHCl3. When electrode was made of stainless steel, distance between electrodes was 20 mm, V（Cl2）:V（CH4）= 1.2:1, residence time was 60 s, pulse discharge voltage was 17.5 kV and discharge frequency was 80 Hz, the conversion of CH4, the total selectivity and total yield of CH2Cl2 and CHCl3 were 11.21%, 39.75% and 4.46%, respectivety.
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