In this paper, we propose a new slip boundary condition in hypersonic gas flow simulations. It is derived by considering the Langmuir isotherm adsorption into the Kaniadarkis et al. model of the kinetic theory of gas. Moreover, the motion of the adsorbed molecules over the surface (i.e. surface diffusion) is considered for the calculation of the mean free path in new slip condition. Three aerodynamic configurations are selected for evaluating new slip condition such as (1) the sharp-leading-edge flat plate, (2) circular cylinder in cross-flow, and (3) the sharp 25°–55° biconic cases. Hypersonic gas flows have the Mach number ranging from 6.1 to 15.6, and the working gases are argon and nitrogen. The simulation results show that new slip condition predicts better slip velocity than the Maxwell slip condition and gives good agreement with the direct simulation Monte-Carlo data for all cases considered in the present work.