Network polysilsesquioxane spheres made solely of poly (vinylsilsesquioxane) (PVSQ) and poly(3-mercaptopropylsilsesquioxane) (PMPSQ) were prepared from heterogeneous mixtures of triethylamine (TEA), water, and either vinyltrimethoxysilane (VTMS), or 3-mercaptopropyltrimethoxysilane (MPTMS). The microscopic, macroscopic observations, and the relationship between the diameters of spheres and the amount of each ingredient in the reaction system, showed that spheres formed via a mechanism similar to emulsion polymerization and suspension polymerization, I depending on the reaction conditions. Diameters of spheres could be controlled from tens of nanometers to a few micrometers by adjusting the amounts of TEA, water, and a surfactant. Heating aqueous solutions of metal ions with these spheres produced polysilsesquioxanes (PSQ)-metal nanoparticle composite spheres. The spheres prepared in this study were characterized by scanning electron microscopy, transmission electron microscopy, solid state NMR spectroscopy, IR spectroscopy, elemental analysis, and differential thermal analysis. These spheres would be useful in recovering metals from their ionic solutions and probes after chemical modifications.