Conversion of CO2 with CH4 into liquid fuels and chemicals in a single‐step catalytic process bypassing the production of syngas remains a challenge. In this study, one‐step synthesis of liquid fuels and chemicals (e.g. acetic acid, methanol, ethanol and formaldehyde) from CO2 and CH4 has been achieved at room temperature (30 oC) and atmospheric pressure for the first time using a novel plasma reactor with a water electrode. The total selectivity to oxygenates was ca. 50‐60%, with acetic acid the major component at 40.2% selectivity, the highest value reported for acetic acid so far. Interestingly, direct plasma synthesis of acetic acid from CH4 and CO2 is an ideal reaction with a 100% atom economy, but it is almost impossible via thermal catalysis due to the significant thermodynamic barrier. The combination of plasma and catalyst in this process shows great potential for manipulating the distribution of different liquid chemicals.