Studies presented in this paper concern wide issue of thermal comfort of protective clothing. The Computer Aided Design (CAD) software tools to analyze thermal insulation of multilayer textile assembly used in thermal protective clothing were applied. First, 3D geometry and morphology of a real textile assembly was modeled. In the designed model different scales of resolution were used for individual layers, ranging from a homogenized nonwoven fabrics model to mapping the geometry of yarns in woven fabrics model. Next, the finite volume method to estimate thermal insulation properties of this assembly, when exposed to heat radiation, was used. Finally, the simulation results were verified experimentally using method described in EN ISO 6942. On the basis of both simulation and experimental results obtained for the multilayer textile assembly, protective clothing parameters directly affecting the ability to protect against heat, were determined. Correlating simulated and experimental values of these parameters were obtained, which may indicate that applied software can be an effective tool in analyzing thermal properties of newly designed multilayer functional clothing.