The aim of study was to investigate the influence of kaolin on the physical properties and utility of film produced from native starch. The work involved measurements of strength, structure, and thermal properties. The films were prepared by the casting method. Composite films with 0%, 5%, 10%, and 15% kaolin additives were examined. Measurements of mechanical properties were carried out using the uniaxial tensile test, the nanoindentation test, and nanoscratching. Surface properties were examined by atomic force microscopy and contact angle measurements. Structure was determined by the X-ray diffraction method, and thermal properties were determined by differential scanning calorimetry. A significant influence of kaolin on the strength parameters and thermal and barrier properties of composite films was found. An increase in kaolin content reduced the tensile strength, Young’s modulus, and Poisson’s ratio. Structural analysis showed a partial intercalation and the layered arrangement of kaolin particles. Kaolin additives increased the barrier properties of water vapor in composite films of about 9%. Biopolymer modification by nanoclay reduced the thermal stability of composite films by 7% and could accelerate the biodegradation process. Increasing the concentration of kaolin in the biopolymer matrix led to heightened surface roughness (approximately 64%) and wettability of the surfaces of the film composites of 58%.