Novel radial single-crystalline ZnS nanowire bundles were successfully synthesized via a facile solvothermal route in the presence of triethylenetetramine (TETA). TETA, which was employed for the first time as a growth-orientator for nanoarchitectures, plays a significant role not only for the development of one-dimensional nanostructures, but also in favor of the formation of radial profile. A dynamic ligand-assisted growth mechanism was proposed and demonstrated in detail. Furthermore, the photoluminescence properties of the as-prepared products were studied. The radial ZnS nanowire bundles were found to exhibit enhanced photoluminescence emissions in visible region compared with that of parallel ones and their bulk counterparts, indicating their potential applications for fabricating novel optoelectronic devices. (C) 2009 Elsevier B.V. All rights reserved.