The surface tension of the spinning solution is an important parameter in the electrospinning process. Surfactants can change the surface tension of the solution. In this paper, four different kinds of surfactants were added into 10 wt% polyvinyl alcohol/water solution. The effect of different surfactants on the solution properties, the morphology of the resulting mats, the thermal performance, and the inner structure of nanofibers were investigated. The results showed that the surface tension of the spinning solution decreased significantly when the surfactant content was less than 1 %. The viscosity and electric conductivity of the solution increased with the increasing of cationic and anionic surfactant content. The fiber diameter of poly(vinyl alcohol) mats remarkably decreased from 405 to 100 nm as the non-ionic surfactant content within the range of 1 % (v/v) increased. Besides that, the surfactant content also had some influence on the thermal performance and inner structure of nanofibers. With the surfactant content increasing, both the heat of fusions and crystallinity increased significantly.