Accurate aerothermal prediction under hypersonic flow conditions is crucial for any thermal protection materials design and engineering. The surface catalytic effect, where dissociated atoms recombine into their molecular forms at the air-solid interface, is an exothermic reaction and plays an important role in high-enthalpy aerodynamic environment prediction. Taking SiC, a widely recognized high-temperature thermal protection material as an example, a multiscale fusion approach for aerothermal prediction is proposed. The approach utilizes reactive molecular dynamics method to construct an interface catalysis model, and the Bayesian maximum entropy to integrate experimental and simulational data into an optimized database. Subsequently, using the radial basis function neural network algorithm, a machine learning-based reaction kinetics model with precise analysis of surface catalysis is trained. The obtained catalytic recombination efficiency is used as a boundary input for computational fluid dynamics simulation, enabling rapid and accurate prediction of hypersonic thermal environment. The result shows that the predicted surface heat flux by this novel approach is consistent with the benchmark studies, but comes with significantly reduced computation time. The stagantion heat flux predictions based on the assumptions of full catalytic wall, finite rate catalytic wall (from the proposed multiscale fusion method), and non-catalytic wall are determined to be 8.65×106 W/m2, 7.51×106 W/m2, and 4.02×106 W/m2, respectively. Comparing these with the wind tunnel benchmark value of 7.48×106 W/m2, the error from the proposed multiscale fusion method is 0.30 %, indicating significant enhancement in prediction accuracy through the proposed upscaling method. The new approach could not only reveal complex exothermic reaction processes at the interface, but also enhance the prediction accuracy at much higher computational efficiency, providing an alternative for multiscale modeling of complex flow and heat transfer at the interface.