This study aimed the characterization of the films casted from the aqueous mixtures of the pH induced complexes between silk fibroin (SF) and hyaluronic acid (HA). The insoluble and transparent films were subjected to scanning electron microscopy (SEM) analyses to show the morphological changes. Thermal analysis of complex films was determined by a differential scanning calorimeter (DSC). The changes in the crystalline state were monitored by X-ray diffractometer (XRD) and Fourier transform infrared spectroscopy (FTIR). It was shown that the complexation between HA and SF was dominantly induced by pH. It was shown that the complex films comprised mixtures of crystalline and non-crystalline regions.