The surface structure of the electrospun polymer fibers depends on the polymer concentration, the type of solvent used, applied voltage and so on. To make a desired surface, it is important to understand the effects of the physicochemical properties to form a stable Taylor cone and jet dispensation. We observed the formation of Taylor cone and a consequent structure of fiber by controlling the parameters of applied voltage, solution concentration, solvent and collector effectively. Once the surfaces were fabricated, the structures were analyzed using optical imaging technologies. As the solution concentration was increased, the smooth fibers were formed. In addition, different solvent ratios determined the viscosity and the surface tension of solutions. As a result, with decreased viscosity and increased surface tension, thin fibers were obtained by electrospinning. Furthermore the aligned nanofiber was successfully created by using drum collector.