Naturally occurring nanomaterials are finding growing interests in tailoring properties of engineering polymers for advanced applications. The objective of this study was to develop environment-friendly nanocomposite films by reinforcing kaolinite nanofillers (1–10 wt%) in silicone rubber (SR) matrix using a simple solvent casting technique. Kaolinite-reinforced films showed substantial improvement in mechanical (tensile strength, Young’s modulus, and elongation at break) and thermal properties at very low filler loading (5 wt%). The improvement of solvent resistance nature of the fabricated films was another critical aspect of this study. Unfilled SR film showed ~19% weight loss when immersed in toluene for 4 h at 25 °C, whereas only ~4% weight loss was recorded in the case of 5% (w/w) kaolinite loaded film. Therefore, kaolinite has the potential to bring significant improvement in the properties of SR. This study indicates that there is plenty of room at the bottom for proper utilization of the potential of kaolinite for developing SR-based composite materials for potential applications in many industries, such as textile, household cleaning, construction, electronics, automotive, medical, etc.