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A series of poly (vinyl alcohol) (PVA)/chitosan (CS) blend nanofibrous membranes with different weight ratio of PVA to CS were fabricated by electrospinning method. The morphology, diameter, and structure of electrospun nanofibers were investigated by scanning electron microscopy (SEM), fourier transform infrared (FT-IR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). SEM images showed that the morphology and diameter of the nanofibers were mainly affected by concentration of the blend solution, weight ratio of the blend, respectively. FT-IR, XRD, and DSC demonstrated that there were strong intermolecular hydrogen bonds between the molecules of CS and PVA. The crystalline microstructure of the electrospun fibers was not well developed.