A blend of chitosan and viscose rayon was investigated. A film was made from regenerating the blend of chitosan and viscose rayon. The film was characterized by various techniques, including Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM). The phase behavior of the blend is influenced by its composition with or without carboxymethylated chitosan (CM-Cs). Characterization of the chitosan/viscose rayon (Cs/VR) blend by DSC and DMA suggests partial compatibility of chitosan with VR and lack of compatibility in the remaining cases. Results of the TEM show that the addition of CM-Cs into the blend can improve the compatibility of Cs with VR.