Chitosan/poly(vinyl alcohol)(PVA) blend films with non-toxicity, biodegradability, and biocompatibility were prepared by solvent blending method. The weight composition ratios of chitosan/PVA blend films were 100/0 (chitosan homopolymer), 75/25, 50/50, 25/75, and 0/100 (PVA homopolymer). Physicochemical properties of the prepared blend films according to various blend ratios were investigated by using universal testing machine, thermogravimeter (TGA), differential scanning calorimeter (DSC), wide angle X-ray diffractometer (WAXD), Fourier transform infrared (FTIR) spectrometer, and scanning electron microscope (SEM). The tensile stress and tensile strain of chitosan/PVA blend films increased as the amount of PVA increased. The thermal stability increased with increasing chitosan content in the chitosan/PVA blend films. The DSC curve of the PVA film shows an endotherm peak around $230^{circ}C$, and the peak became smaller and broader with increasing chitosan content. The diffraction intensities of chitosan observed at 2 theta of $10^{circ}$ decreased with increasing the content of PVA in the blend films, but the crystal intensities of the blend films increased as the amount of PVA increased. In the infrared spectra, the absorption band for -OH and -NH stretching vibrations in chitosan broadened and shifted obviously to lower wavenumber with the increase of PVA. Water-retention values of the chitosan/PVA blend films increased as the amount of PVA is increased owing to the hydrophilic nature of PVA. From the structural analyses, it is believed that chitosan and PVA are miscible due to the strong intermolecular hydrogen bonding.