Many chemical and physical properties of materials are depended to a large extent on crystal shape and size. Here, single crystals of selenium with different morphologies and structures were generated through a solvothermal crystallization process using four kinds of readily available solvents (CS2, ethanol, benzene and pyridine). Bulk crystals of beta-phase monoclinic selenium could be easily obtained in CS2 while rod-Eke trigonal selenium crystals with different dimensions and aspect ratios could be produced in the other three kinds of solvents. When ZnCl2 was added into the pyridine system, very long trigonal selenium fibers (generally longer than 2mm) could be fabricated in relatively short-time period. The structural features of as-grown crystals were characterized by scanning electron microanalyzer and X-ray diffraction techniques. The formation processes of different selenium crystal structures are discussed. (C) 2002 Elsevier Science B.V. All rights reserved.