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Abstract This study presents the main principles of the free radical photopolymerization reaction. Photoinitiators and photoinitiating systems are reviewed, and their most important features are discussed. Attention is paid to sources of light, particularly light‐emitting diodes (LEDs), which are discussed with respect to the absorption properties of commercially available photoinitiators (PI). The mechanism of free radical photopolymerization is also reviewed, with a focus on simulation models. Characterization techniques are described, demonstrating that the final properties can be analyzed, as well as the polymerization process and side effects such as oxygen inhibition. Finally, the different families of monomers usable in free‐radical photopolymerization are presented, together with the main properties of the corresponding photopolymers.