The thermal and mechanical properties of polysiloxane foam are greatly improved by the addition of acrylolsobutyl polyhedral oligomeric silsesquioxane (MA0701, hereinafter referred to as MAPOSS), which has double bonds. The morphologies and properties of the polysiloxane composite foam were characterized. The average cell diameter of the composite foams decreased, while the cell density increased with increasing MAPOSS. Meanwhile, MAPOSS can enhance thermal conductivity and thermal stability. Thermal conductivity increased by 25%, and the temperature at the maximum weight loss rate increased from 556 °C to 599 °C. In addition, MAPOSS also promoted heterogeneous nucleation by functioning as a nucleating agent, which can increase cell density to improve the mechanical properties. The compressive strength of the composite foam increased by 170% compared with that of pure foam. In the composite, MAPOSS increased the cross-linking density by acting as a physical cross-linking point and limited the movement of the segments.