Porous silicone composites containing different types and volume fractions of hollow silica particles (HSPs) were prepared and characterized in terms of thermal insulation performance, thermal stability, and tensile and dynamic mechanical properties. The comparative study on measured and theoretical thermal conductivity of porous silicone/HSP composites was performed. Dependence of shell thickness, defined as the ratio (η) of internal (ri) to outer (r0) radius, and volume fraction (Φ) of HSPs on the thermal insulation performance of composites was predicted theoretically by Felske model. Tensile properties and dynamic mechanical measurements showed the incorporation of HSPs led to mechanical reinforcement in the silicone composites. Theh Guth and Gold equation showed mechanical reinforcement of porous silicone/HSP composites was primarily due to the hydrodynamic effect of HSPs in the silicone matrix at low HSP contents (Φ < 0.5).