Catalytic and radiative effects at the interface of high-enthalpy flow and thermal protection materials play a crucial role in the generation of aerodynamic thermal loads of high-speed aerospace vehicles. However, traditional thermal protection system designs usually employ empirical correction methods to account for these effects, with insufficient quantitative characterization of the material’s catalytic and radiative temperature-dependent effects. A viscous wall-boundary treatment method considering the material’s catalytic-radiative temperature-dependent effects is proposed and incorporated into a chemical non-equilibrium solver, thereby establishing a coupled catalytic-radiative chemical non-equilibrium aerodynamic thermal prediction method. Cylinder flow simulations revealed temperature-dependent catalytic-emissivity effects: Catalytic coefficient increases induced synchronized 39% rises in stagnation heat flux and wall temperature, while elevated emissivity reduced wall temperature but increased heat flux (~10%). Optimal materials require low catalytic efficiency (γ < 0.01) coupled with high emissivity (ε > 0.8). Numerical evaluations of five materials demonstrated stagnation heat flux ranking: Cu > SiC > UHTC > Si > SiO₂, with inverse wall temperature trends. Nonlinear catalytic-radiation interactions induced regional performance deviations, highlighting material-specific thermal management complexities. This research establishes theoretical foundations for application-specific thermal protection material design and performance optimization across diverse aerospace operational environments.