Electrospun fabrics for use in, for example, tissue engineering, wound dressings, textiles, filters and membranes have attracted a lot of attention due to their morphological nanoscale architectures which enhance their physical properties. A thorough detailed internal morphological study has been performed on electrospun polystyrene (PS) fibers produced from dimethylformamide (DMF) solutions. Investigations by transmission electron microscopy (TEM) and thorough studies for the first time by synchrotron based X-ray tomographic microscopy (XTM) revealed that the individual electrospun PS fibers and beads have a graded density and in some cases even an internal porous structure.