The conversion of CO₂ with CH₄ into liquid fuels and chemicals in a single‐step catalytic process that bypasses the production of syngas remains a challenge. In this study, liquid fuels and chemicals (e.g., acetic acid, methanol, ethanol, and formaldehyde) were synthesized in a one‐step process from CO₂ and CH₄ at room temperature (30 °C) and atmospheric pressure for the first time by using a novel plasma reactor with a water electrode. The total selectivity to oxygenates was approximately 50–60 %, with acetic acid being the major component at 40.2 % selectivity, the highest value reported for acetic acid thus far. Interestingly, the direct plasma synthesis of acetic acid from CH₄ and CO₂ is an ideal reaction with 100 % atom economy, but it is almost impossible by thermal catalysis owing to the significant thermodynamic barrier. The combination of plasma and catalyst in this process shows great potential for manipulating the distribution of liquid chemical products in a given process.

The direct synthesis of H₂O₂from H₂and O₂using Pd catalyst, fuel cell and plasma methods have been reviewed systematically.

Due to the increasing emission of carbon dioxide (CO₂), greenhouse effects are becoming more and more severe, causing global climate change. The conversion and utilization of CO₂ is one of the possible solutions to reduce CO₂ concentrations. This can be accomplished, among other methods, by direct hydrogenation of CO₂, producing value-added products. In this review, the progress of mainly the last five years in direct hydrogenation of CO₂ to value-added chemicals (e.g., CO, CH₄, CH₃OH, DME, olefins, and higher hydrocarbons) by heterogeneous catalysis and plasma catalysis is summarized, and research priorities for CO₂ hydrogenation are proposed.