Glycerol is the main by-product of biodiesel production. For this reason, its valorization into value-added products, by using green procedures, represents an important goal. Different sulfonic acid silica- or titania-based catalysts were prepared, characterized and tested in the glycerol etherification process, assisted by microwaves, in order to obtain biodiesel additives. The surface and structural properties of the catalysts were investigated by means of N2 adsorption isotherms, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and acid capacity measurements by X-Ray Fluorescence Spectroscopy (XRF). The best performance in terms of activity was achieved in the presence of the sulfonic function directly linked to the amorphous silica. By the correlation of the structure properties of the materials and their activity, the performance of the catalysts was shown to be influenced mainly by the surface area, pore volume and acidity. Recycling experiments performed over the most active systems showed that the sulfonic silica-based materials maintained their performance during several cycles.