In this work, silicone/alumina composites with 33 wt.% silicone content are prepared by compression mould technique. TGA, XRD and SEM were used to characterize the ceramifying behavior when the samples were heated from 600 to 1600°C. XRD results suggest that the ceramic residue of SR could restrain the phase transformation of γ-Al2O3 below 1100°C, indicating that the chemical bonds preserve the mechanism strength of SR/Al2O3 composites under high temperature. The flexural strength increases from 18.19 MPa to 75.31 MPa with the increasing temperature from 600 to 1600°C, owing to the sintering reaction between SiO2 and Al2O3 forming mullite phase under higher temperature. It has low liner shrinkage after firing and nearly no macrocracks or deformation under any temperature, illustrating that the SR/Al2O3 composites can be used as organic fire-retardancy materials.