Green mussel shells (Perna viridis) are generated in huge amounts and discarded as waste materials. Such waste may be used to produce biopolymer materials such as chitosan. The physicochemical properties of chitosan prepared from different sizes of green mussel shells (small size (CHS): ≤5.00 cm in length and big size (CHB): >5.01 cm in length) were characterized and compared with commercial chitosan (CH). Furthermore, the mechanical and physicochemical properties of the blended films were also investigated. The results of the physicochemical properties showed that CHS and CHB were quite different from CH. The degree of deacetylation of CHS, CHB, and CH was found to be 32.71%, 52.56%, and 70.42%, respectively (p < 0.05). The water- and fat-binding capacities of CH were higher than those of CHS and CHB. Structural differences between CHS, CHB, and CH were studied using Fourier transform infrared spectroscopy (FTIR) and X-ray powder diffraction (XRD). Significant increases in thickness, water vapor permeability, and strength of the blended films were found when the extracted chitosan was added (p < 0.05). However, further study is needed to improve the chitosan extraction process, which can enhance the physicochemical properties of the obtained chitosan and be widely used in many industries.