Electrospinning is a method to prepare nanoscale fiber from polymer solutions. The present work focuses on the influence of molecular weight of polymer and the relationship between the morphology and solution viscosity in the electrospinning of poly(vinyl aceate) (PVAc). Polymer solution properties such as the viscosity and the surface tension were measured by viscometer and tensiometer, respectively. Also, electrospun PVAc web was characterized via scanning electron microscopy (SEM) and universal testing machine (UTM). The fiber diameter depended on the electrospinning parameters such as the molecular weight of polymer and the viscosity. Also, PVAc fibers with analogous average diameters resulted when the, spinning solutions had similar viscosity in spite of the different molecular weights of PVAc used. The fiber diameter increased with increasing viscosity. As linear velocity of the drum collector surface in the MD (machine direction) was faster than that of the CD (cross direction), electrospun fibers had a tendency to be arranged toward MD. As a result, the mechanical properties such as yield stress and tensile strength of MD were higher than those of CD.