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This paper explores the modeling of physical phenomena that occur in clothing that affect the safety and biophysical comfort of the user. Three-dimensional models of textile assemblies with complex morphology used in firefighters’ multilayer protective clothing were designed in a CAD environment. The main goal of the research was to design and experimentally verify (by thermography) the models in terms of simulations when the heat transfer occurs through them in selected ambient conditions using the finite volume method. The designed models took into account the subtle differences in the geometry of selected assemblies determined by high-resolution X-ray microtomography. The designed models made it possible to calculate heat transport with a difference of about 2% to 5% in comparison to experiment that depend on the ambient conditions and the complexity of the model geometry. Moreover, the comparison of the simulation results with the experimental outcomes shows that the mapping of subtle differences in the internal structure of the assemblies in the designed models allows us to observe differences in the modeled heat transfer.