The integration of metal oxide nanomaterials with mesoporous silica is a promising approach to exploiting the advantages of both types of materials. Traditional synthesis methods typically require multiple steps. This work instead presents a fast, one-step, template-free method for the synthesis of metal oxides homogeneously dispersed within mesoporous silica, including oxides of W, Ti, Nb, Ta, Sn, and Mo. These composites have tunable metal oxide contents, large surface areas, and wide mesopores. The combination of Nb2O5 nanoparticles (NPs) with SiO2 results in an increased surface area and a larger number of acid sites compared to pure Nb2O5 NPs. The surface texture and acidity of the silica–niobia composites can be tuned by adjusting the Nb/Si molar ratio. Moreover, the silica provides protection to the niobia NPs, preventing sintering during thermal treatment at 400 °C. The silica–niobia materials exhibit superior performance as catalysts in the aldol condensation of furfural (Fur) with acetone compared to pure niobia, leading to an up to 62% in product yield. Additionally, these catalysts show remarkable stability, retaining their performance over multiple runs. This work demonstrates the potential of the proposed synthesis approach for preparing more sustainable, high-performance, durable, and stable nanoscale metal oxide-based catalysts with a tunable composition, surface area, and active site density.