Electrospun fibers were produced using a variety of solvents to investigate the influence of polymer/solvent properties on the fiber surface morphology. Electrospinning is a novel processing technique for the production of fibers with diameters in the range of a few nanometers to tens of micrometers. We have been able to produce polymeric fibers with a high surface area through the introduction of a micro- and nanostructured surface structure, which we refer to as a "porous" morphology. These features could be introduced in several different polymeric fibers increasing their range of application significantly. The pores vary from densely packed, well-formed nanopores with diameters in the range 20-350 nm to larger flat pores,of about 1 mum. The increased surface area of polymeric fibers was correlated with high volatility solvents used in the electrospinning process. The effect of processing parameters on the fiber surface morphology was also investigated using optical microscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM).