AbstractA key component in light‐induced radical polymerization is the photoinitiator which produces free radicals through a photochemical reaction. In the first part of this paper, a short analysis of the different steps that take place in the light‐induced radical polymerization using bimolecular photoinitiating systems is made. In the second part, the obtained results in the polymerization of acrylic monomers using conjugated and nonconjugated aminobenzophenones as photoinitiators are shown. A summary of the photochemical behavior of these photoinitiators together with several aspects related to the polymerization kinetics are described. The nature and efficiency of the produced radicals are studied as well as the reactivity of the radicals generated from the substituted dimethylanilines‐camphorquinone photoinitiation systems. Important mechanistic differences were found in the photochemical behavior and radical efficiency for the families of photoinitiators studied.