Cross-linking and structurable polymer photosensitive materials have been studied for many years and they are widely used for optical recording of information. After the investigation of the photo-chemical and photo-physical processes in various systems, it appears that the chemical structure of the polymer matrix plays an essential role in the process of reaction that takes place upon irradiation by a laser beam. The results of experiments that were conducted to investigate the modification of the absorption with the time of exposure, modification of the degree of photo-structuring with time, the dependence of the photosensitivity on thickness and other characteristics are presented in this paper. Some of the applications of the results concerning the hardening of the cross-linking polymers with the scope to improve the mechanical properties of the surface relief image (hardness, strength, adhesive stability) and the possibilities to make copies by the hot stamping method are also presented