Light induced polymerization reaction is employed in quite different technical applications that have become beneficial to humans. These applications include microelectronics, information technologies, optical fibers, dental materials, printing inks, paints, varnishes, ... In other words, various kinds of polymers can be synthesized by light-induced chemical processes, a technique commonly denoted by the term photopolymerization. A key component of this process is the photoinitiating system, which is responsible of the absorption of light and its conversion into chemical energy. Among these applications, photopolymer materials have revealed to be the best choice for holographic recording, promoting holography as a compelling choice for nextgeneration data storage needs. In holography and display devices, photopolymers were developed primarily for display of single images due to the refractive index variations or relief profiles generated by an optical interference pattern. Compared to inorganic photorefractive materials, photopolymers have much higher sensitivity due to chemical amplification effects, large dynamical range, high versatility of the formulations. In this paper, a set of photoinitiating systems (PIS) for free radical photopolymerization was studied using time-resolved spectroscopic experiments, real-time FTIR for 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 dye/coinitiator system by virtue of a photocyclic behaviour. Homogeneous photopolymerization process was found to reach 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.