In spite of great concern on the industrial application of microcellular silicone rubber foams, such as in electric and medical devices, only a few works can be found about the foaming of silicone rubber. In this study, microcellular silicone rubber foams with a cell size of 12 μm were successfully prepared with curing by heat and foaming by supercritical CO2 as a green blowing agent. The microcellular silicone rubber foams exhibited a well-defined cell structure and a uniform cell size distribution. The crosslinking and foaming of silicone rubber was carried out separately. After foaming, the silicone rubber foam was cross-linked again to stabilize the foam structure and further improve its mechanical properties. Foaming process of cross-linked silicone rubber should be designed carefully based on the viscoelastic properties because of its elastic volume recovery in the atmosphere. The basic crosslinking condition for small cell size and high cell density was obtained after investigating the rheological behavior during crosslinking.