Electrospinning is a technique use to fabricate ultrafine fibers with diameters in the nanometer range. The electrospun fiber mats have high potentials for many applications, due to their high surface area to volume, high porosity and small pore size. In this study, chitosan-ethylenediaminetetraacetic acid (CS-EDTA)/polyvinyl alcohol (PVA) blend nanofibers were successfully prepared using electrospinning techniques without organic solvent. CS was dissolved in EDTA aqueous solution and then blended with PVA solution at various weight ratios. Physicochemical properties of CS-EDTA/PVA solution such as viscosity, conductivity and surface tension were investigated. The morphology and diameter of the electrospun fiber mats were analyzed by using scanning electron microscopy (SEM). The composite structure was characterized by differential scanning calorimetry (DSC) and fourier transform infrared spectroscopy (FT-IR). SEM images showed that the morphology and diameter of the nanofibers were mainly affected by the weight ratio of the blend. Nanofibers were obtained when the CS-EDTA content was less than 50%wt. The average diameter of the nanofibers was 119-223 nm, and this average diameter decreased with increasing CS-EDTA content. In summary, these CS electrospun nanofiber mats may be proper for the drug delivery or wound dressing application.