Numerical method for predicting the aero-heating environment of hypersonic vehicles with catalytic surface is developed by solving the multispecies chemical nonequilibrium Navier-Stokes equations. A catalytic-efficiency-based finite-rate catalytic boundary condition including ionic species is proposed to model the surface catalysis. Then numerical simulations with different surface catalytic efficiencies of a reentry capsule are conducted to investigate the influence of finite-rate surface catalysis on aero heating. Results show that the surface catalytic efficiency plays a significant role in aero-heating, and low catalytic efficiency material should be adopted to ease the aero-heating environment. Compared with the convective heat flux, the cliff usi ve heat flux is more sensitive to the catalytic efficiency, and is the main mechanism of the nonlinear increase in aero-heating. Beside the surface catalytic efficiency, the influence of surface catalysis on aero-heating also depends on the local flow characteristics, such as degree of dissociation and ionization, surface density, temperature, and so on. [ABSTRACT FROM AUTHOR]