In this chapter, a compilation of different systems able to photogenerate active radicals toward polymerization reaction( type I, type II and three component photoinitiating systems) for application in holographic grating recording when associated to monomers is reviewed. In particular, the visible curable system is associated to fluorinated acrylate monomers formulation for creation of transmission gratings. The PIS efficiencies are presented in term of diffraction grating yields and compared to photopolymerization experiments. The special case of photocyclic initiating systems is described in details, its influence on the grating built up being discussed on the basis of selected mixtures using visible dyes, electron donors (e.g. amines), electron acceptors (e.g. iodonium salts) or hydrogen donors as coinitiators. The role of the photochemical properties of dye on the performance of the holographic recording material is investigated through time resolved and steady state spectroscopic studies of the PIS (e.g. nanosecond laser flash photolysis), to highlight the photochemistry underlying active radicals photogeneration. In order to get more insight into the hologram formation, grating formation curves were compared to those of monomer to polymer conversion obtained by real time Fourier transform infrared spectroscopy (RTFTIR). This work outlines the importance of the coupling between the photoinitiating system (i.e. the photochemical reactions) and the holographic resin.