Thermal desorption spectroscopy (TDS) under ultra high vacuum (UHV) condition has been used to investigate the desorption characteristics of Cu/CeO2/gamma-Al2O3 thin film catalysts coated onto the microchannel of a microreactor. TDS results demonstrate that surface desorption profiles and chemical properties (acid-base and redox properties) are remarkably influenced by the catalyst composition, i.e. the loading of copper and ceria. The enhanced basicity with the increase of ceria loading and the decrease of copper loading is evident from the shifted desorption maximum of CO2 in TDS spectra. Three oxygen species, ranging from weakly bound oxygen desorbed at low temperature to the strongly held lattice oxygen desorbed at high temperature, are easily discernible and clearly identified by O-2 TDS spectra, depending on the catalyst compositions. The concomitant thermal desorption of O-2, CO2, and H2O at low temperature indicates the unique chemical properties of copper/ceria catalyst with appropriate copper and ceria contents. The observed low-temperature feature is ascribed to the role of porthole of copper/ceria interfacial area for several desorbed species. The weakly bound oxygen species is attributed to the enhanced abundance of copper/ceria interfacial anionic vacancies created by the intimate contact between copper and ceria entities and its impact on steam reforming of methanol (SRM) reaction is tentatively discussed in terms of reverse oxygen spillover.