The effect of electrode materials on the co-generation of syngas and higher hydrocarbons from CO2 and CH4 using dielectric-barrier discharge has been investigated. The electrode materials tested here include aluminum, copper, steel, and titanium. For the feed of methane in the absence of CO2, the order of activity of methane conversion from high to low was Ti≈ Al > Fe > Cu, while the order of the activity of CO2 conversion was Al > Cu > Ti > Fe for the case of CO2 feed without methane. Regarding the co-feed of methane and CO2, the titanium electrode shows the best activity for the conversions, while the other three materials show a similar performance for the conversions. The effect of dilution gas, helium, on the conversions has also been discussed.