The response of a semi-infinite compressible fluid to a step-wise change in temperature of its boundary is investigated analytically and numerically. Numerical results of the boundary layer structure are compared with Clarke’s analytical solution for a gas with thermal conductivity proportional to temperature. To avoid unwanted numerical dissipation in the numerical analysis, the space-time conservation element and solution element (CESE) method has been adopted to solve the unsteady 1-D Navier-Stokes equations. Good agreement between analytical and numerical results has been found for the development of the thermal boundary layer on a long time scale. Weak shock waves and expansion waves induced by the thermal boundary layer due to its compressibility, are observed in the numerical simulation. Finally, the numerical method has been applied to the reflection of a non-linear expansion wave and to a shock wave from an isothermal wall, thereby illustrating the effect of the boundary layer on the external flow field.