The electrospinning process is a fascinating method to fabricate small nanosized fibers of diameter several hundred nanometers. Surfactant-polymer solutions were prepared by adding poly(vinyl alcohol) (PVOH) to distilled water with cationic, anionic, amphoteric, and non-ionic surfactants. Average diameter of the electrospun PVOH fibers prepared from PVOH solution was over 300 nm, and was decreased to 150 nm for the mixture of PVOH/amphoteric surfactant. To explain the formation of ultra fine fiber, the characteristic properties in a mixture of PVOH/surfactant such as surface tension, viscosity, and conductivity were determined. In this paper, the effect of interactions between polymers with different classes of surfactants on the morphological and mechanical properties of electrospun PVOH nonwoven mats was broadly investigated.