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The ESR spectra of catalyst V2O5/γ-Al2O3 and its activity for the dehydrogenation of isobutane were investigated. On the basis of the results of the ESR spectroscopy associated with the TPR results, it is suggested that there is a strong interaction between V2O5 and γ-Al2O3 and the V4+ species on the surface is the active center of catalyst V2O5/γ-Al2O3 for this reaction.