The ability of clothing to provide protection against external environments is critical for wearer’s safety and thermal comfort. It is a function of several factors, such as external environmental conditions, clothing properties and activity level. These factors determine the characteristics of the different microclimates existing inside the clothing which, ultimately, have a key role in the transport processes occurring across clothing. As an effort to understand the effect of transport phenomena in clothing microclimates on the overall heat transport across clothing structures, a numerical approach was used to study the buoyancy-driven heat transfer across horizontal air layers trapped inside air impermeable clothing. The study included both the internal flow occurring inside the microclimate and the external flow occurring outside the clothing layer, in order to analyze the interdependency of these flows in the way heat is transported to/from the body. Two-dimensional simulations were conducted considering different values of microclimate thickness (8, 25 and 52 mm), external air temperature (10, 20 and 30 °C), external air velocity (0.5, 1 and 3 m s−1) and emissivity of the clothing inner surface (0.05 and 0.95), which implied Rayleigh numbers in the microclimate spanning 4 orders of magnitude (9 × 102–3 × 105). The convective heat transfer coefficients obtained along the clothing were found to strongly depend on the transport phenomena in the microclimate, in particular when natural convection is the most important transport mechanism. In such scenario, convective coefficients were found to vary in wavy-like manner, depending on the position of the flow vortices in the microclimate. These observations clearly differ from data in the literature for the case of air flow over flat-heated surfaces with constant temperature (which shows monotonic variations of the convective heat transfer coefficients, along the length of the surface). The flow patterns and temperature fields in the microclimates were found to strongly depend on the characteristics of the external boundary layer forming along the clothing and on the distribution of temperature in the clothing. The local heat transfer rates obtained in the microclimate are in marked contrast with those found in the literature for enclosures with constant-temperature active walls. These results stress the importance of coupling the calculation of the internal and the external flows and of the heat transfer convective and radiative components, when analyzing the way heat is transported to/from the body.