Mesostructured silica-nanoparticle monolithic composites have been synthesized by dispersing prefabricated nanoparticles of gold or zeolite (silicalite) in ethanolic reaction mixtures containing SiCl4 and a Pluronic triblock copolymer template. Whereas silicalite nanoparticles were used directly, surface functionalization of the gold nanoparticles with either primed silicate ions or a discrete 3-5-nm-thick silica shell was required to increase the interfacial compatibility with the hydrophilic poly(ethylene oxide) blocks. Under these conditions, the resulting monoliths consisted of distributed nanoparticles within an ordered mesostructured silica matrix. Removal of the polymer template by calcination produced corresponding mesoporous silica-nanoparticle replicas. The combination of the structure and the porosity of the silica framework with the crystal chemical properties of the embedded nanoparticles suggests that such composites should be useful as multifunctional materials.