Chitosan/poly(ethylene oxide) (PEO) blends of different component ratios, in the form of films, have been prepared. Structure, hydrophilicity, morphology and thermal behavior of the samples have been examined by Fourier transform infrared spectroscopy (ATR-FTIR), contact angle measurements, atomic force microscopy (AFM) and differential scanning calorimetry (DSC).The studies revealed weak interactions between chitosan and PEO suggesting immiscibility of the components in the blends. However, stronger interactions owing to hydrogen bonding between blend components were found for chitosan/PEO (80/20) blend.Morphology of the blend surfaces was affected by the crystallinity of PEO and was dependent on the sample composition.