To seek an efficient route for syngas production from oxidative CO2 reforming of methane (OCRM) via post-plasma catalytic technique, three routes were compared using spark-shade plasma (input power = 106 W, with F1 of 1.36 SLM at CH4:O2:CO2 = 1:0.6:0.7) and Ni/CeO2/Al2O3 catalyst (catalyst temperature = 800 °C, with or without F2 of 0.52 SLM CH4). Compared with Route 1 (plasma only, F1 only), and H2/CO ratio of Route 2 (plasma + catalyst, F1 only) increased to 100%, 99%, 76% and 1.2, respectively; but kept at about 35%, which was close to the thermodynamic-equilibrium values. In Route 3 (plasma + catalyst, F1 + F2), increased dramatically to 67%, and H2/CO ratio further increased to 86% and 1.5, respectively, though decreased to 77%. Both SCO and arrived at nearly 100%. Assuming that the plasma could supply the heat energy for the subsequent catalytic reaction at 800 °C, syngas energy cost as low as 0.5 eV/molecule and energy efficiency as high as 91% were achieved.