In this work, different kinds of silane coupling agents modified expanded graphite (MEG) fillers were successfully prepared and then incorporated into silicon rubber matrix to fabricate flame-retardant composite materials (SR/MEG). The inserted MEG fillers with siloxane chains exhibited good compatibility with the silicon rubber matrix, which cannot only reduce the negative impact of adding fillers on mechanical properties but also endow the silicon rubber composites with ideal flame retardancy. Subsequently, platinum (Pt) catalyst was incorporated into the SR/MEG composites to prepare SR/MEG/Pt composites, and the synergistic effects of MEG and Pt catalyst on the thermal stability, flame retardancy, and combustion behavior of silicon rubber composites were systematically investigated. The target SR/MEG/Pt composite with appropriate addition of MEG and Pt catalyst can obtain relatively high char residue of 41.9% and limiting oxygen index value of 29.6%, as well as achieve V-0 rating in the vertical combustion test, owing to the formation of expanded and dense silicon–carbon protective layer under the catalysis of Pt catalyst. Moreover, the cone calorimeter test results showed that the peak of heat release rate and total heat release of SR/MEG composites were further reduced after the addition of an appropriate amount of Pt catalyst, manifesting the good synergistic effect of MEG and Pt catalyst on the flame retardancy performance of silicon rubber. The method proposed herein may provide a promising way for fabricating high-performance flameretardant silicone rubber materials.