Abstract: The aerodynamic heat load on the surface of the non-ablative thermal protection materials which served in the chemical non-equilibrium flow field, is controlled by the coupling of chemical non-equilibrium degree of flow field and the surface catalytic reaction of the materials. If the coupled effect is neglected in the performance simulation, the effective service performance cannot be obtained through the ground simulation test. Therefore, according to the stagnation-point heat flux relationship within the boundary layer of the blunt body supersonic vehicle, the present paper analyzes the principal flow field parameters, the characteristics of high-enthalpy supersonic field provided by ground simulation equipment, and the differences between ground and flight environments. The validity of the Three-Parameter-Simulation method is analyzed by the CFD simulation. A Four-Parameter-Simulation method is presented for analyzing the heat transfer of the chemical non-equilibrium stagnation-point boundary layer. Besides, the properties of the thermal protection materials is analyzed and a preliminary solution is proposed when the dissociation enthalpy in the Four-Parameter-Simulation is unable to be simulated.