We discuss the photon activation of structural relaxations in glassy melts and frozen glasses containing molecules that can photoisomerize. The built-in stress following a photoinduced electronic transition lowers the thermal activation barrier for subsequent structural reconfiguration of the glassy matrix. We provide explicit predictions for the barrier distribution and structural relaxation spectrum as functions of the concentration of photoactivated molecules and the fragility of the material. The typical barrier decreases upon photoactivation, while the barrier distribution increases in width with increasing mole fraction of photoactive molecules and fluence, and becomes multimodal. In a frozen glass, the initial effects of photoisomerization locally facilitate the dynamics near the excited chromophores and can lead to complete fluidization at a sufficiently high fluence. Photon activation initially decreases the yield strength of the glass. Depending on the precise time course of illumination, there however emerges a spatial coexistence of softened regions with regions that, after being destabilized by illumination, have reconfigured so that they are now made of ultrastable glass or have crystallized as in a porcelain. This sequence of events, after illumination, can lead to highly stable amorphous solids, potentially approaching the Kauzmann limit. These mechanisms are at the root of optical information storage technologies in amorphous materials.