Polymeric ablative materials (PAMs) are widely used in spacecraft currently for thermal insulation. However, it is challenging to find a single filler that can improve both ablative and mechanical properties of PAMs. In this study, a new type of hybrid cross‐linked polyphosphazene microspheres (PHC) is added to ethylene propylene diene monomer (EPDM) composites as a filler for the first time and its influence on the ablation, mechanical, and thermal properties of EPDM is investigated. The results show that the addition of 3 phr PHC increases the ablation performance by about 10% and enhances the mechanical properties by 20% approximately. In addition, the ablation mechanism is studied in accordance with SEM, FTIR, and Raman spectroscopy. On the one hand, PHC has the effect of catalyzing carbonization, thus increasing the rate of residual carbon; on the other hand, PHC changes the morphology of the char layer, forming a cross‐linked structure containing P─O─Si bonds on the surface. The findings regarding catalyzing carbonization and the special char layer structure could guide the design of ablative materials.