The effect of solvents on the surface morphology and mechanical properties of poly(vinyl acetate) nanofibrous nonwoven via electrospinning was investigated. The fiber diameters decreased with increasing boiling point of the solvents. Among the solvents used in this study, DMF was the best solvent that produced PVAc fibers with the thinnest diameter of ca $0.2;{mu}m$. Such a result can be explained by considering the high boiling point of a solvent, allowing sufficient time for a smaller segment of a charged jet during its flight to the collector.