There is an increasing interest in applying the technology of electrospinning for making ultrafine fibers from biopolymers for food-grade applications, and using pullulan (PUL) as a carrier to improve the electrospinnability of proteins and other naturally occurring polyelectrolytes. In this study, PUL solutions containing NaCl or Na3C6H5O7 at different concentrations were electrospun. The inclusion of salts interrupted the hydrogen bonding and altered solution properties, such as viscosity, electric conductivity, and surface tension, as well as physical properties of fibers thus obtained, such as appearance, size, and melting point. The exogenous Na+ associated to the oxygen in the C6 position of PUL as suggested by FTIR measurement and was maintained during electrospinning. Bead-free PUL fibers could be electrospun from PUL solution (8%, w/v) in the presence of a 0.20 M NaCl (124 ± 34 nm) or 0.05 M Na3C6H5O7 (154 ± 36 nm). The further increase of NaCl or Na3C6H5O7 resulted in fibers that were flat with larger diameter sizes and defects. SEM also showed excess salt adhering on the surfaces of PUL fibers. Since most food processing is not carried out in pure water, information obtained through the present research is useful for the development of electrospinning biopolymers for food-grade applications.