The aim of this study was to prepare and characterize membranes of silk fibroin (SF) and chitosan (CHI) blends. Moreover, a conformation transition of SF to a more stable form induced by the addition of CHI was verified. Blend membranes were prepared, after pH adjustment, in different ratios, and physical integrity, crystallinity, structural conformation and thermal stability were characterized. The results of crystallographic analysis (XRD) indicated the tendency to higher structural organization caused by the addition of CHI. Fourier transformed infrared spectroscopy (FTIR) showed that SF is present in a more stable form in the presence of a CHI content of only 25 wt%. Thermal analysis indicated that SF is thermally stable and that when its proportion in the blend increases, the temperature at which degradation is initiated also increases.