The surface and bulk structure and composition of a commercial V-W-Ti oxide catalyst used for denitrification of waste gases from power plants has been investigated by XRD, XRF, ICP, TG-DTA, FT-IR and SEM-EDS analyses and by comparison with ’model’ catalysts. The catalyst powder consists of a full ’monolayer’ of surface complexes, mainly constituted by wolframyl species with the addition of small amounts of vanadyl and sulphate species over high-area TiO2-anatase. The characteristics of the surface vanadyl, wolframyl and sulphate species fully consist with those previously reported for model V-Ti, W-Ti, V-W-Ti and sulphated titania catalysts. The catalyst powder is mixed with glass-like particles, playing the role of mechanical promoters. The possibility of contamination of the catalyst particles by Mg or other alkali or alkali earth cations possibly arising from the glass particles during monolith preparation and during reactor start-up and shut-off procedures as well as during catalyst operation is suggested.