A series of Ce-Mo oxide catalysts with different Ce/Mo atomic ratio were prepared and applied to selective oxidation of toluene to benzaldehyde. The structures and properties of the surfaces of catalysts were characterized by XRD, TPR and DR-UVS. The natures of oxygen species on the surfaces of these samples were studied by using temperature programmed desorption-mass spectrography(TPD-MS). The results showed that the oxygen species of multiple adsorption existed on the sample surface. And in the range of desorption temperature<900℃, for the Ce-Mo samples, not only the desorption peaks of O- species on surfaces of samples be discoved, but also the O2- species appeared. As the content of Ce in Ce-Mo oxides was changed, the activation energy of oxygen desorption(Ed) also changed. The Ed value of sample 3 (Ce/Mo=1/1) is the lowest and its selectivity of benzaldehyde in toluene oxidation is the highest. Thus, a Parallel relation between the Ed value and the selectivity for benzaldehyde existed in these Ce-Mo oxides.