Electrospinning gives rise to polymer nanofibers. The spinning process is characterized by strong deformations of the polymer material taking place during the spinning process and a very rapid structure formation process happening within milliseconds. We were interested in the influence of the peculiar spinning process on the structures of nanofibers. For this purpose, we analyzed the internal structures of nanofibers spun from polyamide-6 and polylactide with an average diameter of about 50 nm. The fibers were partially crystalline, with degrees of crystallinity not significantly smaller than those found for less rapidly quenched and much thicker melt-extruded fibers. The annealing of polyamide fibers at elevated temperatures resulted in a transformation from the disordered T modification to the more highly ordered a modification, and this again was in close agreement with the response of melt-extruded fibers. The orientation of the crystals along the fiber axis was strongly inhomogeneous: it was, on average, very weak, yet it could be quite pronounced locally. Small elongations of approximately 10% resulted in well-developed homogeneous crystal orientations. (C) 2003 Wiley Periodicals, Inc.