The present article presents an overview of photopolymerization reactions and is focused on photoinitiators, photosensitizers, radical and cationic monomers and oligomers, the film photopolymerization of acrylates, epoxides, vinyl ethers, thiol–enes, waterborne light‐curable systems, UV powder formulations, charge‐transfer monomers, dual cure and hybrid cure systems, the general functional properties of the cured materials, the applications, etc. The kinetics, the monitoring of the photopolymerization, the investigation of the excited state processes, the access to the rate constants of the chemical reactions, the solution and bulk reactivity, and the photochemical and chemical reactivity are also discussed.