Oxygen chemisorption experiments on prereduced silica-supported vanadia catalysts have been performed in order to determine the optimum conditions for measuring the relative dispersion of vanadium oxide on the silica substrate. By following the extent of vanadia reduction microgravimetrically, it is shown that an appropriate prereduction of the catalyst at 823 K under hydrogen is fundamental in obtaining a reproducible well-defined stoichiometrically reduced vanadium oxide system (V3+). AT 643 K the reduction process is very much slower and requires very long times in order to approach a plateau. Measurement of the binding energies of the V2P(3/2) core level spectra indicates that high-temperature oxygen chemisorption (643 K) results in a reoxidation of the prereduced vanadium oxide species within crystallites leading to an overestimation of the number of exposed vanadium sites. Chemisorption at low temperatures (298 or 195 K) does not affect the stoichiometrically reduced vanadium oxide species within crystallites, thus allowing the number of exposed surface vanadium sites to be measured.