Copper/cerium bimetallic catalyst is an efficient material for the removal of carbon monoxide, while the rapid deactivation under moisture-rich conditions in the conventional thermal-catalysis limited its wide application. Here, we investigated the plasma-assisted catalytic oxidation of CO over Cu/Ce oxides supported on γ-Alumina in comparison with the conventional thermal catalytic oxidation. The TOF values of the Cu/Ce catalysts showed that the plasma catalysis was the better catalytic system for CO oxidation (2.96 s−1 for thermal catalysis, 5.13 s−1 for plasma catalysis). Importantly, the energy barriers for plasma catalysis were much lower than that for thermal catalysis, especially under moisture-rich conditions (e.g. 130.3 kJ/mol versus 246.1 kJ/mol under 9.8 vol% water vapor). The loss of activity caused by water was reversible for the plasma process, but not for the thermal process. The Cu/Ce catalyst remained good stability within 60 h in the presence of 6.1% water for plasma oxidation, while the thermal catalytic activity declines gradually. Also, water could inhibit the formation of gas byproducts (O3 and NOx). The promoting role of plasma could be mainly ascribed to the enhanced strength of oxygen mobility and plasma-assisted decomposition of surface carbonate in the presence of water, as revealed by the in-situ NTP-TPR, XPS, and the ex-situ DRIFTS analyses.