In this study, regenerated Antheraea mylitta silk fibroin (ASF) and Polyvinyl alcohol (PVA) dissolved in formic acid were blended together in variable ratios. The rheological properties of the solutions were analyzed and the structure-property relationship of blend films prepared using these solutions followed by coagulation in methanol was studied. The blend films were tested for their morphological and structural analysis using scanning electron microscopy (SEM), Fourier Transformed Infrared (FTIR), and X-ray diffraction (XRD) techniques. The influence of blending on thermal and mechanical properties was studied through Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), and Dynamic Mechanical Analysis (DMA) respectively. The structural and thermal properties indicated interaction amongst the polymeric chains of silk and PVA with no visible phase separation. The biodegradability, water uptake capacity, and biocompatibility of blend films were tested and found to have influenced by blending. The synergistic enhancement of the functional properties due to alterations in the structure of polymer blends was observed. The blend films presented high viability of L929 fibroblast skin cells seeded on them as calculated by alamar blue assay. The attachment of cells was observed on the film surfaces and the proliferation of cells towards attaining their conventional morphology after 48 hrs of seeding was visualized via SEM indicating excellent biocompatibility of films. The as-prepared blend films with remarkable properties can potentially be used in the biomedical field for tissue engineering applications.