Photopolymerization technology has gained prominence as an attractive alternative to traditional thermal polymerization processes due to variety of advantages and benefits. The evolution in the laser technologies areas allow the use of visible light emitting lasers for applications such as, holography, laser direct imaging, stereolithography due to lower cost and good performances. However, the design and study of very efficient visible light photoinitiating systems is still challenging. One promising way toward high performance materials are three-component photoinitiating visible light systems, based on redox properties of additives. The reaction mechanism of these systems based on a dye, an oxidant coinitiator and a reductant coinitiator are not very well understood. As an example, the photopolymerization efficiency and the mechanistic reactivity of photoinitiating systems based on a dye, an amine and a redox component was studied using time-resolved spectroscopic experiments, real-time FTIR and holographic recording. It is shown that the efficiency of the photoinitiating system can be drastically increased when a redox additive is added to the conventional bicomponent dye/coinitiator system by virtue of a photocyclic behavior. Moreover, the mechanism of reaction and the photopolymerization efficiency depend on the redox properties of added coinitiator. RT-FTIR spectroscopy experiments show a homogeneous photopolymerization process with a fast vitrification, limiting the conversion at about 55%. By contrast, holographic recording underlines the differences in photoinitiating system reactivity, allowing diffraction efficiencies close to unity for the most reactive PIS.