The thermoporosimetry method was adapted to determine the mesh size distribution of an acrylate thermoset clearcoat. This goal was achieved by increasing the solvent rate transfer by increasing the pressure and temperature. A comparison of the results obtained using this approach with those obtained by DMA (dynamic mechanical analysis) underlined the accuracy of thermoporosimetry in characterizing the macromolecular architecture of thermosets. The thermoporosimetry method was also used to analyze the effects of photoaging on cross-linking, which result from the photodegradation of the acrylate thermoset. It was found that the formation of a three-dimensional network followed by densification generates a modification of the average mesh size that leads to a dramatic decrease of the meshes of the polymer.