The categories and applications of ablation thermal protection materials for space exploration have been reviewed， including high density glass fiber reinforced phenolic plastics， honeycomb reinforced ablation thermal protection materials， PICA and PICA-X， high density carbon phenolic of US， and nylon phenolic， honeycomb reinforced ablation thermal protection materials and NF material of China. The applied space exploration probe， aerodynamic heating environment， the properties and manufacture technology of the thermal protection structure are introduced. The anomaly ablation cases of the materials and the selected materials change of US space exploration are summarized. It can be seen that the coupling relationship between thermal protection material and heat environment is complex. The research of thermal protection material on resisting anomaly damage in our country is presented. The application and development of the thermal protection materials for space exploration are prospected in the end.