Thiol-modified silica and silsesquioxanes are of interest as adsorbents tailored for chalcophilic metals. High capacity adsorbents must have high surface area to access the thiol functionalities and to give an effective adsorbent. High capacity adsorbents should be possible by polymerizing thiol-modified triethoxysilanes, but the polymerizations fail to generate sufficient connectivity to form high molecular weight polymers, let alone form gels. This research looks to the incorporation of thiols into hybrid organic-inorganic gels using a tetrasulfide monomer that is reductively cleaved in the gel to afford the desired thiol-modified material. While the tetrasulfide monomer does permit gels to form, its relative flexibility allows the gels to collapse during drying resulting in non-porous xerogels. Here we describe our efforts to engineer the architectures in these sol-gel materials to obtain the maximum level of thiol functionalization in a high surface area material as potential metal adsorbents.