A series of modified VOx/MSU-1 catalysts were prepared using MSU-1 as the supports, and then were used to catalyze the oxidative dehydrogenation of isobutane to isobutene with CO2. The reaction results showed that the addition of La or Ce could increase the catalytic activity of VOx/MSU-1. La2O3-VOx/MSU-1 was systematically characterized by XRD, H2-TPR and NH3-TPD methods and it was found that the La2O3 addition could improve not only the dispersion of VOx species, active components, over MSU-1 support but also the acid-base properties of catalysts surface, which was favorable to the oxidative dehydrogenation of isobutane. The optimal reaciton conditions were obtained, under which isobutane conversion was 63.6% and isobutene yield was 52.3%. At last, It was demonstrated by the stability experiments of 8 h that La2O3-VOx/MSU-1 possessed higher catalytic stability than VOx/MSU-1.