The total oxidation of trichloroethylene (TCE) in air at low relative humidity (RH = 10%) in the presence of CO2 (520 ppmv) was investigated in function of energy density using an atmospheric pressure negative DC luminescent glow discharge combined with a cryptomelane catalyst positioned downstream of the plasma reactor at a temperature of 150 °C. When using Non-Thermal Plasma (NTP) alone, it is found a low COx (x = 1–2) yield in agreement with the detection of gaseous polychlorinated by-products in the outlet stream as well as ozone which is an harmful pollutant. Introduction of cryptomelane enhanced trichloroethylene removal, totally inhibited plasma ozone formation and increased significantly the COx yield. The improved performances of the hybrid system were mainly ascribed to the total destruction of plasma generated ozone on cryptomelane surface to produce active oxygen species. Consequently these active oxygen species greatly enhanced the abatement of the plasma non-reacted TCE and completely destroyed the hazardous plasma generated polychlorinated intermediates. The facile redox of Mn species associated with oxygen vacancies and mobility as well as the textural properties of the catalyst might also contribute as a whole to the efficiency of the process.