Photomagnetism in molecular systems is a new development in molecular magnetism. It traces back to 1982 and 1984 when a transient effect and then the light-induced excited-spin-state-trapping effect was discovered in spin-crossover complexes. The present contribution gives a definition of the phenomenon, a process that changes the magnetism of a (molecular) system after absorption of a photon. It is limited to the discussion of photomagnetism based on metal-metal electron transfer in clusters and extended molecule-based magnets. The paper is organized around the main pairs of spin bearers, which allowed us to evidence and to study the phenomenon: Cu-Mo, Co-Fe, and Co-W. For each metallic pair, we report and discuss the conditions of appearance of the effect and its characteristics, both in extended structures and in molecular units: structure, spectroscopy, magnetism, thermodynamics and kinetics, and applications. We conclude with some brief prospects. The field is in rapid expansion. We are convinced that the interaction of photons with magnetized matter, to provide original magnetic properties, will meet more and more interest in the future.