Large (mm-cm) free-standing CdSe/ZnS core/shell quantum-dot networks (gels, xerogels, and aerogels) with high luminosity have been synthesized by oxidative removal of surface thiolate ligands from preformed core/shell particles. In contrast to analogous poorly emissive networks prepared from "naked" CdSe nanoparticles, the extent of quantum confinement in the 3-D connected solid is a function of the precursor particle size and shows little dependence on the network density.