In this work, chitosan-polyethylene glycol (Cs/PEG) blend films with different mass ratios have been synthesized utilizing simple blending and casting technique. Molecular structure, electronic transitions and surface morphology of the developed blends have been inspected utilizing a series of Fourier Transform Infrared (FTIR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM). Moreover, both of the microhardness and swelling ability of the blends with different mass ratios have been evaluated. Both of UV-Vis and FTIR results postulates the presence of a distinct sort of interaction between both of chitosan (Cs) and polyethylene glycol (PEG) which could emanate from the newly formed intermolecular hydrogen bonds between Cs and PEG. It was also found that increasing PEG mass ratio in the blend results in increasing the value of the direct bandgap. SEM micrographs of the blend revealed changing the surface morphology of chitosan after the addition of PEG.