Solid acid catalysts based on WO₃–SiO₂ and WO₃–ZrO₂–SiO₂ were prepared by one-pot non-hydrolytic sol–gel method and tested in the gas phase glycerol dehydration to acrolein. Their structural and textural characteristics were determined by X-ray diffraction (XRD), N₂ adsorption, X-ray energy dispersive spectroscopy (XEDS), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Their acid characteristics were studied by both temperature programmed desorption of ammonia (NH₃-TPD) and FTIR of adsorbed pyridine. Under our operating conditions, all the catalysts were active and selective in the transformation of glycerol to acrolein, which was always the main reaction product. The high selectivity to acrolein is achieved on catalysts presenting a higher proportion of Brønsted acid sites. In addition, the role of oxygen in the feed on catalytic performance of these catalysts is also discussed.