Electrostatic spinning or electrospinning is a process by which a high electrical potential is applied to a polymer solution or melt across a finite distance between a nozzle and a collective target to produce ultrafine fibers with diameters in the sub-micrometer down to nanometer range. In this research work, the effects of various solution parameters (i.e. concentration, average molecular weight of the polymer, solution temperature, solvent systems and added salt) and process parameters (i.e. electrostatic field strength and emitting electrode polarity) on morphological appearance and average size of electrospun polyamide-6 (PA-6) fibers were investigated using optical scanning (OS) and scanning electron microscopy (SME) techniques. For the investigation of solution parameters based on the solution properties (i.e. viscosity, surface tension and conductivity) characterizing, it was found that these properties were important factors on the morphology and the diameter of the fibers obtained. For the investigation of process parameters, the morphological appearance and the diameter between fibers obtained from positive or negative polarities were differences. The as-spun PA-6 fibers from negative polarity were flat with average size being much larger than those from positive polarity which appeared to be round.