Two series of WOx/TiO2 catalysts, containing W surface densities up to 4.4 W atoms/nm(2), were prepared by pore volume impregnation of two different supports, titanium oxyhydroxide (amorphous) or titanium oxide (crystallized, 100% anatase). The influence of W surface density and the nature of the support on the surface structure, development of the acidity, and catalytic performances were examined. The texture and structure of the catalysts were investigated by Brunauer-Emmett-Teller measurements, X-ray diffraction (XRD), and Raman and infrared spectroscopy. The catalytic activity was tested for 2-propanol dehydration and n-hexane isomerization. For catalysts obtained by impregnation of titanium oxide, XRD and Raman results showed that W was present as a surface phase. Infrared spectra indicated an increase in the degree of polymerization of W species with increasing W surface density. CO and lutidine adsorption, followed by infrared spectroscopy, showed an increase in the strength and abundance of Bronsted acid sites (measured after lutidine desorption at 573 K) with the W surface density above a threshold of 1.3 W atoms/nm2. The development of Bronsted acidity correlated with the evolution of the infrared bands attributed to polymerized W species. A direct relationship was observed between the concentration of Bronsted acid sites and the catalytic activity for 2-propanol dehydration. Catalytic activity, for n-hexane isomerization, appears to be associated with the presence of highly condensed W species. The catalysts synthesized by impregnation of titanium oxyhydroxide exhibited a comparable behavior. Hence, for a given W surface density, the W surface structure, concentration of Bronsted acid sites, and catalytic performances were similar. Thus, no significant effect of the initial form of the support (titanium oxyhydroxide versus titanium oxide; 100% anatase) was evidenced.