Three vanadium pyrophosphate catalysts have been prepared by calcining vanadium hydrogen phosphate hemihydrate (VOHPO4.0.5H(2)O, prepared in an organic medium) for different lengths of time (40, 100 and 132 h) in a n-butane (0.75%)/air mixture at 473 K. The catalysts were designated VPO40, VPO100 and VPO132. Increasing the duration of reaction with n-butane/air mixture led to an increase in the total surface area from 21.3 m(2) g(-1) (VPO40) to 24.9 m2 g-1 (VPO100) and to 27.0 m(2) g(-1) (VPO132). It also led to the complete removal of the VOPO4 phase from catalysts VPO100 and VPO132, this VOPO4 phase having seen as a minor component of catalyst VPO40. Scanning electron microscopy showed that longer periods of pretreatment in the n-butane/air mixture produced catalysts with increasing amounts of a characteristic rosette-type of agglomerate. Temperature-programmed reduction with HZ resulted in the removal of similar to 11 monolayers equivalent of oxygen from all three of these catalysts at a peak maximum temperature of similar to 1000 K with the development of a second reduction peak at similar to 1100 K which increases with increasing time of n-butane/air pretreatment. The morphology produced by extended pretreatment in the n-butane/air mixture at 673 K is therefore predisposed to reaction with HZ (and probably with n-butane). Apparently paradoxically, increasing the duration of n-butane/air pretreatment results in catalysts which on temperature-programmed desorption desorb less oxygen.