Gasification of biomass, followed by ZrO2-catalyzed hot gas clean-up at 600–900 °C for the oxidation of impurities (such as tar), is an environmentally attractive way to produce heat and power or synthesis gas. The interaction of toluene (as a model compound for tar) with ZrO2-based gasification gas clean-up catalysts was studied by in situ DRIFTS and temperature-programmed gas-phase analysis. Toluene was found to interact in four ways with ZrO2 surfaces: forming molecularly adsorbed toluene, surface benzoate species, carbonaceous deposits and surface benzyl species. The adsorption of toluene in the absence of gas-phase oxygen at ambient temperature on ZrO2-based catalysts resulted in weakly adsorbed molecular toluene, while the adsorption of toluene at higher temperatures yielded carbonaceous deposits and surface benzoate species. Combined analysis of infrared and TP data showed that some of the benzoate species decomposed, producing benzene and carbon dioxide. Surface benzyl species, on the other hand, were detected on the surface of ZrO2-based catalysts only in the presence of gas-phase oxygen at a temperature where toluene and oxygen started to convert. Therefore, it is suggested that benzyl species are the active intermediates from toluene to carbon oxides during the gasification gas cleaning over ZrO2-based catalysts.