A plasma-catalytic reactor consisting in a vertical coaxial dielectric barrier discharge reactor filled with solid catalysts was developed to directly synthesize liquid chemicals (alcohols, acids, hydrocarbons) and syngas from CO2 and CH4 at atmospheric conditions. Co and Fe catalysts prepared via incipient wetness impregnation method were loaded on a SiO2 aerogel support synthesized by ambient drying method after surface modification. Discharges were generated in different ratios of CO2/CH4 mixtures at ambient conditions and the performance of the catalysts was evaluated. In this study, the total liquid selectivity was approximately 40% after introducing the catalysts, where main liquid products were methanol and acetic acid. By varying the CH4 and CO2 ratio, a small number of long-chain hydrocarbons and alcohols were also detected with our catalysts. The synergy of plasma-catalysis in this process demonstrates great potential for the direct synthesis of value-added liquid chemicals and fuels from CO2 and CH4.