A technique based on the use of an ArF excimer laser (193 nm) to analyze the morphology of the unsaturated polyester and vinylester networks has been developed. This method is based on the use of the differences between the thresholds at which ablation of the various constituent phases of the materials occurs. After having determined the ablation threshold of a polystyrene, various surface treatments using excimer lasers fluence around this threshold were applied to unsaturated polyesters and vinylester. In the latter case, a two-phase structure consisting of microgels in a polystyrene phase was shown by scanning electron microscopy observations, allowing us to conclude that the mechanisms by which vinylester and unsaturated polyester networks are formed are similar. We also observed that the two-phase structure of the vinylester matrixes, unlike that of the unsaturated polyesters, is organized rather than random-structured, which could represent a major parameter contributing to the very good hydrolysis stability of these materials. In the event of degradation by osmotic mechanisms, the organized structure network would enable limiting of the development of the osmotic pressures by distributing the forces within the material, thus avoiding crazing.