In this study, the effects of the addition of glyoxal cross-linker and sodium chloride (NaCl) salt on the solution properties (conductivity, surface tension, viscosity), spinning performance and fiber properties (diameter and diameter uniformity) in roller electrospinning of poly(vinyl alcohol) (PVA) are discussed. According to the results, solution conductivity, viscosity and fiber diameter increase with the addition of glyoxal cross-linker and NaCl salt. On the other hand, the spinning performance of PVA increases with cross-linking treatment, but decreases as the NaCl salt concentration increases. In addition, there is no relation between NaCl concentration and fiber diameter uniformity. Generally, high fiber density, fine and uniform PVA nanofibers were obtained via the roller electrospinning method.