Silica-based spherical macrostructures containing vanadium and tungsten oxides were prepared using anion exchange resin beads as a shape-directing macrotemplate in a multi-step procedure. In a first step resin beads were treated with a clear and homogeneous TPA-silicate synthesis solution at 170 °C for three different times and resin-silicate composites were obtained. Short treatment times resulted in amorphous silica whereas the longest time yielded highly crystalline silicalite-1. In a second step anionic vanadium or tungsten species were introduced into the resin-silicate composites by utilization of the residual ion exchange capacity of the resin. In a final step the ion exchange resin was removed by calcination leaving behind vanadium- or tungsten-containing silica spheres. The influence of the concentration and the pH of the solutions used for vanadium and tungsten ion exchange on the properties of the final spheres was investigated. The product particles were extensively characterized by XRD, SEM, AAS, nitrogen adsorption measurements, Raman and UV–vis diffuse reflectance spectroscopy. Generally, the nature of the metal species formed within the spheres was isolated and highly dispersed monomers in tetrahedral coordination in amorphous samples and V2O5 or WO3 crystallites in crystalline ones.