The further improvement of methacrolein (MAL) selectivity from isobutene (IB) oxidation is crucial and challenging. In this study, based on the typical MoeBieFeeCoeKeO mixed metal oxide, the rare earth element Gd-doped, Ce-doped and CeGd co-doped catalysts were prepared by co-precipitation strategy to increase the selectivity of MAL from 47.9% to 49.8%, 64.2% and 68.6%, respectively. In order to elucidate in-depth the promoting effect of Ce and/or Gd, various characterizations were utilized including X-ray diffraction patterns (XRD), Raman, X-ray fluorescence spectrometry (XRF), X-ray photoelectron spectroscopy (XPS), O2-temperature programmed desorption (O2-TPD), H2-temperature programmed reduction (H2-TPR), CO2-temperature programmed desorption (CO2-TPD), IB-temperature programmed desorption (i-C4-TPD) and in-situ IB-Fourier transform infrared spectroscopy (IB-FTIR). Both Ce and Gd finely regulate the bulk and surface structure of the catalyst, thus altering the redox ability, oxygen mobility and storage ability and basicity. Compared with Ce, Gd addition slightly regulates the variation of Co2þ/Co3þ redox couples, greatly enhances the interaction among the components on the catalyst, thus only increases the content of surface oxygen species and has little effect on their mobility. While Ce containing catalyst performs stronger oxygen storage and migration ability, thus leading to the overproduction of surface Odefect species, which are proposed to be the active sites for the production of MAL and COx. The CeGd co-doped catalyst possesses the proper content of surface Odefect species, thus exhibits much higher MAL selectivity. Moreover, the promoting mechanism of Ce and/or Gd over IB oxidation is proposed. Therefore, this work is helpful for understanding the influence of rare earth elements on the structure of mixed metal oxides and the olefin selective oxidation reaction.