We present an innovative approach for reacting carbon dioxide and water to give syngas by combining heterogeneous catalysis and non-thermal plasma techniques. This approach utilizes an abundant water and nickel catalyst, and mitigates the thermodynamic penalty by using a Dielectric Barrier Discharge (DBD) plasma reactor. Argon dilution was used in the experiment to reduce the exothermic recombination of hydrogen and oxygen, which is considered as the major hurdle for H2O conversion. As a result, the syngas ratio was dramatically improved from 0.07 to 0.86. In addition, the conversions of CO2 and H2O were improved by packing Ni/γ–Al2O3 catalysts into the DBD reactor. The yields of H2 and CO were up to 13.8% and 5.6% respectively. The conditions for plasma catalysis and the catalyst characterization are presented and discussed.