In the re-entry process of the vehicle into the atmosphere, the high-temperature environment, induced by the compression of the strong shock wave and viscous retardation, is created around the head of a vehicle. These generate a conductive plasma flow field, which provides a direct working environment for the application of magnetohydrodynaimic (MHD) control technology. Numerical simulations based on thermochemical non-equilibrium MHD model are adopted to analyze the surface heat flux of an orbital reentry experiment (OREX) vehicle. The influences of wall catalytic conditions on the aerothermal environment under different flight conditions are discussed. In addition, the control mechanism of an external magnetic field on high-temperature thermochemical non-equilibrium flow field is analyzed. The results show that the distribution of surface heat flux monotonically increases with the catalytic recombination coefficient increasing, and the surface heat flux rises and then drops with the flight altitude decreasing. Moreover, the wall catalytic properties significantly affect the efficiency of MHD control technology, and the total heat flux is closely related to the accumulation of atomic components, diffusion gradient and temperature gradient near the wall region. With an external magnetic field applied, the accumulation of oxygen atoms and nitrogen atoms near the wall can be reduced. Moreover, the Lorentz force can increase the shock standoff distance, and then reduce the component diffusion gradient and wall temperature gradient. Under three different wall catalytic conditions, the ability to control the surface heat flux MHD is ranked from strong to weak as fully catalyzed, partially catalyzed and non-catalyzed.