The role of ozone was studied for two different configurations combining non-thermal plasma (NTP) and heterogeneous catalysis, namely the use of a gas phase plasma with subsequent exposure of the effluent to a catalyst in a packed-bed reactor (post-plasma treatment) and the placement of the catalyst directly in the discharge zone (in-plasma catalysis). Non-porous and porous alumina and silica were deployed as model catalysts. The oxidation of immobilised hydrocarbons, toluene as a volatile organic compound and CO as an inorganic pollutant were studied in both operational modes. While conversion and selectivity of hydrocarbon oxidation in the case of catalytic post-plasma treatment can be fully explained by the catalytic decomposition of O-3 on γ-Al2O3, the conversion processes for in-plasma catalysis are more complex and significant oxidation was also measured for the other three materials (α-Al2O3, quartz and silica gel). It became obvious that additional synergetic effects can be utilised in the case of in-plasma catalysis due to short-lived species formed in the NTP. The capability of porous alumina for ozone decomposition was found to be correlated with its activity for oxidation of carbon-containing agents. It could be clearly shown that the reaction product CO2 poisons the catalytic sites at the γ-Al2O3 surface. The catalytic activity for O-3 decomposition can be partially re-established by NTP treatment. However, for practical purposes the additional reaction pathways provided by in-plasma catalytic processes are essential for satisfactory conversion and selectivity. © 2004 Elsevier B.V. All rights reserved.