To achieve the sustainable development of the rubber industry, the substitute of carbon black, the most widely used but non-renewable filler produced from petroleum, has been considered one of the most effective ways. The naturally occurring illite with higher aspect ratio can be easily obtained in large amounts at lower cost and with lower energy consumption. Therefore, the expansion of its application in advanced materials is of great significance. To explore their potential use as an additive for reinforcing rubber, styrene butadiene rubber (SBR) composites with illites of different size with and without 3-mercaptopropyltriethoxysilane (KH580) modification were studied. It was found that the modification of illite by KH580 increases the K-illite/SBR interaction, and thus improves the dispersion of K-illite in the SBR matrix. The better dispersion of smaller size K-illite with stronger interfacial interaction improves the mechanical properties of SBR remarkably, by an increment of about nine times the tensile strength and more than ten times the modulus. These results demonstrate, except for the evident effect of particle size, the great importance of filler–rubber interaction on the performance of SBR composites. This may be of great significance for the potential wide use of the abundant naturally occurring illite as substitute filler for the rubber industry.