Polystyrene (PS) dissolved in the mixture of tetrahydrofuran (THF) and N,N-dimethyl formamide (DMF) was electrospun to prepare fibers of sub-micron in diameters. Electropinning parameters such as polymer concentration, applied voltage and tip-to-collector distance were controlled. From these parameters it was determined that while the surface tension of polymer solution had linear correlation with the critical voltage, throughput was dependent on electric conductivity. The electrospun PS fibers produced contained irregular beads and electrospinning certainly was enhanced with increasing DMF content. The bead concentration was also controlled by DMF content. The aspect ratio of the formed beads and the diameter of fibers were increased with increasing solution concentration. When PS was dissolved in only THF, an unexpected half hollow spheres (HHS) structure appeared. Also, different shape forms of PS non-woven mats have been prepared by controlling electrospinning parameters. (C) 2003 Elsevier Science Ltd. All rights reserved.