The ablative properties of epoxy-modified vinyl silicone rubber (EMVSR) composites containing hexaphenoxycyclotriphosphonitrile (HPCTP) have been systematically studied. The strength of the ablation char layer was greatly enhanced with the addition of HPCTP, which induced the formation of a more complete, denser, and thicker char during oxyacetylene ablation tests. Moreover, the HPCTP-containing EMVSR composites demonstrated lower thermal conductivity and pyrolysis rate when compared with those without HPTCP. At the same time, the thermal insulation properties of HPCTP-filled composites were improved under low heat flow ablation scenarios. The reduction of graphitic carbon content, the formation of phosphate-like crystals as well as the increase of SiC content contributed to strengthening the char layer, which was critical for improving the ablation properties. The optimum char layer strength and thermal insulation properties were achieved when the content of HPCTP was 15 phr, whereas an optimum ablation resistance was achieved at 25 phr HPCTP. This suggests that HPCTP-modified EMVSR composites can be used for thermal protection purposes, especially in the fields of aerospace and aeronautics.