Biodegradable materials are used in the manufacture of packaging and compostable films and various types of medical products. They have demonstrated a large number of potential practical applications in medicine and particularly in the treatment of various cardiac, vascular, and orthopedic conditions in adults as well in children. In our research, the extrusion-cooking technique was applied to prepare thermoplastic starch (TPS), which was then utilized to obtain environmentally friendly starch-based films. Potato starch was the basic raw material exploited. Polyvinyl alcohol and keratin were used as functional additives in amounts from 0.5 to 3%, while 20% of glycerol was harnessed as a plasticizer. The processing of the thermoplastic starch employed a single screw extruder-cooker with an L/D ratio of 16. The film blowing process was carried out using a film-blowing laboratory line with L/D = 36. FTIR Spectroscopy was applied for the assignment of the prominent functional groups. The results showed that the processing efficiency of thermoplastic starch with functional additives varied depending on the level of polyvinyl alcohol and keratin addition. Moreover, the FTIR data correlated with the changes in the physical properties of the tested films. The analysis of FTIR spectra revealed several changes in the intensity of bands originating from stretching vibrations characteristic of the –OH substituent. The changes observed depended on the presence/lack of the hydrogen bonding occurring upon interactions between the starch molecules and the various additives used. In addition, notable changes were observed in bands assigned to glycoside bonds in the starch.