Differently prepared (VO) 2 P 2 O 7 phases and an amorphous V 3 + PO catalyst were investigated under conditions of the selective n-butane oxidation and the toluene ammoxidation, respectively, using a self-constructed in situ-ESR flow reactor in the X-band. By examining the temperature dependence and the line shape of the ESR signals exchange integrals as well as the 2nd and the 4th moment were obtained. These parameters characterize the spin-spin exchange behaviour and, thus, structural and electronic disorder of the catalysts. Increasing structural disorder was found to improve the catalytic performance in the n-butane oxidation. For both catalytic processes a significant reversible alteration of the ESR line shape was observed under working conditions which is discussed in terms of a perturbation of exchange interactions between neighbouring vanadyl centres near the surface the oxidation state of which is assumed to fluctuate between +4 and +5 during the catalytic reaction.