The synthesis of semiconductor nanocrystalline networks using weak capping ligands in aqueous media has been demonstrated. Carbohydrates, including β-cyclodextrin, D-(+)-glucose, D-glucosamine, lactobionic acid, sucrose, and starch were chosen as weak ligands to facilitate the formation of PbTe nanoparticle networks. The nanoparticle size, ranging from 5 nm to 30 nm, can be tuned by manipulating the temperature and concentration. Through a similar strategy, more complicated nanostructures including carbohydrate spheres@PbTe core–shell structures and Te@carbohydrate@PbTe multilayered submicron cables have been fabricated. This is a general approach which can be easily extended to the fabrication of other semiconductor networks, including PbSe and Bi₂Te₃ using carbohydrates and ethylenediaminetetraacetic acid (EDTA), respectively, as ligands.