Biodegradable blend films composed of chitosan and PEG with various composition ratios were prepared. The chemical structure of the blend films was characterized with FTIR and X-ray, which showed no chemical bond formations but certain interactions probably coming from the hydrogen bonds. Morphologies of these blend films were viewed using AFM and SEM, suggesting that pure chitosan film had a smooth surface structure and the blend films surface showed a plenty of holes with varying size. Through the DMA measurement, it was found that there existed differences in the peak area and position of the blend films, and the peak at the glass transition temperature became significantly weaker and was markedly wider with the increasing content of PEG. The obtained results showed that the crystallinity of chitosan was suppressed and partially destroyed; and this should have an influence on the thermal behaviors and dynamic mechanical properties of the blend films.