Catalytic oxidation is a widely used pollution control technology for removing volatile organic compounds. Pd-Ce/ZSM-5 catalysts with different Ce contents were prepared by a co-impregnation method, and their catalytic performance was investigated for the oxidation of methyl ethyl ketone (MEK). The by-products of the reaction were monitored using gas chromatography and collected in thermal desorption tubes, which were further analyzed by gas chromatography/mass spectrometry. The PdCe9.6/ZSM-5 catalyst displayed the highest catalytic efficiency, as a consequence of a higher amount of strong acid sites and a superior PdO-Pd redox cycle in the presence of a CeO2 additive. The introduction of CeO2 enriched the by-product species. The formation mechanisms and oxidation routes of typical by-products, such as methyl acetate, 1-penten-3-one and 3-buten-2-one, 3-methyl, during MEK oxidation over Pd-Ce/ZSM-5 catalysts was also analyzed. CH3* species that formed on the catalyst were identified as reaction intermediaries. Trace amounts of acetic acid and methyl vinyl ketone were also detected and were further oxidized to methyl acetate, 1-penten-3-one and 3-buten-2-one, 3-methyl. (c) 2012 Elsevier B.V. All rights reserved.