The flammability behaviors of ammonium polyphosphate/aluminum hydroxide/mica/silicone rubber (APP/Al[OH]3/mica/SiR) ceramifying composites containing APP, Al[OH]3, and mica are investigated by cone calorimeter test. The thermal degradation and the synergistic effect of APP/Al(OH)3/mica/SiR composites are investigated by thermal gravimetric analysis, X‐ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. APP/Al(OH)3/mica/SiR composites with 25 wt% of APP, 20 wt% of Al(OH)3, 25 wt% of mica, and 30 wt% SiR presents a much lower total heat release, the value of peak heat release rate (PHRR), the maximum average heat release rate, the longest time to ignition, and time to the PHRR (tPHRR), compared with the flame‐retardant properties from composites with filler of APP and mica or APP and Al(OH)3 alone. The results indicate that there is an excellent synergism in APP, Al(OH)3, and mica, which endows APP/Al(OH)3/mica/SiR composites with both good flame retardancy and fire prevention. The study on the synergism effect between fire prevention and flame retardancy of APP/Al(OH)3/mica/SiR composites indicates that compounds containing P‐O‐Al are formed due to the reaction between APP and Al(OH)3 during combustion in the early stage and a coherent, dense, and sealed structure is formed due to the reaction in mica, phosphates, and the thermal decomposition products of SiR during combustion in the later stage.