Network polysilsesquioxane (PSQ) spheres of narrow size distribution were prepared from one or mixtures of organotrialkoxysilanes (OTAS) using internal and external catalysts. The spheres were characterized by solid state NMR spectroscopy, IR spectroscopy, elemental analysis, differential thermal analysis, BET, and electron microscopies. The diameters of spheres were controlled from approximately 10 nm to 2 microns by adjusting the amounts of reaction components. These spheres showed a few interesting properties. Above all, heating aqueous solutions of metal ions such as gold, silver, palladium, and platinum with these spheres produced PSQ-metal nanoparticle composite spheres. The nanoparticles were found both inside and on the surface of the spheres. The weight of gold produced by these spheres were estimated by monitoring the amount of Au4+ remaining in the solution that often exceeded the weight of spheres. The PSQ/gold nanoparticles were purple with Ćmax at approximately 550 nm. These particles were expected to be useful for recovering metals from their ionic solutions and probes either as they were or after chemical modification.