This paper presents the characterization of the cellular structure and thermal conduction behaviour of polypropylene foams produced using different foaming processes, with the aim of selecting the best possible PP foam thermal insulator. Thermal conductivity results have shown that the global heat transfer behaviour is controlled by the relative density. For relative densities higher than 0.2, thermal conductivity differences were insignificant, the data being predicted by the mixture's rule and Russell's model. In the low density range, all of the proposed models underestimated the overall conductivity, the effect of the processing method being more significant, slight differences being observed between foams produced by extrusion and those produced by gas dissolution with higher cell sizes and anisotropies. Foams with finer cellular structures showed to be better insulating materials.