Abstract: In order to design thermal protection system, it is important to predict heat transfer rate precisely on the hypersonic vehicles. In present paper, considering chemical reaction, interal energy excitation and thermo-chemical non-equilibrium effects of high temperature air, the thermo-chemical non-equilibrium flow-fields are simulated using the numerical code AEROPH_Flow. An aero-physical numerical code system for hypersonic vehicles, the distributions of heat transfer rate is obtained, and the analysis is done for the influence of the chemical reaction model, thermodynamic non-equilibrium model, surface temperature, surface material catalytic action on the computational results. The results show that thermo-chemical non-equilibrium models have a more important influence on the computational results, it is important for the selection of the correct air reaction model and thermal non-equilibrium model according to the flight environment and thermo-chemical non-equilibrium mechanism of the flow-field around the hypersonic vehicles; the heat transfer rate isn't always the highest for lower surface temperature, and it become very complicated for the variation law of heat transfer rate along with the surface temperature under the condition of high Mach number or thermo-chemical non-equilibrium flow, so the surface temperature may as well be fixed choosed aecording to the distribution of the real flight condition or different constant for computing exactly heat transfer rate on the hypersonic vehicles.