Blend membrane consisting of poly (vinyl alcohol) (PVA) and chitosan was prepared from a solvent-casting technique and characterized for their intermolecular interactions using infrared and X-ray diffraction methods. Cross-linking the blend with glutaraldehyde produces a membrane with lower crystallinity and a smaller swelling degree, but having improved thermostability and mechanical properties. The present blend membrane shows a pH-dependent swelling characteristic and will be discussed in detail.