Rarefied gas flow over a backward-facing step (BFS) is often encountered in separating flows prevalent in aerodynamic flows, engine flows, condensers, space vehicles, heat transfer systems, and microflows. Direct Simulation Monte Carlo (DSMC) is a powerful tool to investigate such flows. The purpose of this research is to assess the impact of Mach number and wall temperature on the flow and surface properties in the transitional flow regime. The Mach numbers considered are 5, 10, 25, 30, and the ratio of the temperature of the wall to that of freestream considered are 1, 2, 4, 8. The Reynolds number for the cases studied is 8.6, 17.2, 43, and 51.7, respectively. Typically the flow properties near the wall are found to increase with both Mach number and wall temperature owing to compressibility and viscous dissipation effects. The variation in flow properties is more sensitive to Mach number than the wall temperature. The surface properties are found to decrease with Mach number and increase with wall temperature. Moreover, in the wake of the step, the vortex’s recirculation length is reasonably independent of both free stream Mach number and wall temperature, whereas it decreases with Knudsen number.