Polymer systems induced by the reaction between monomers and photo-initiators play a crucial role in the formation of volume-phase gratings. In this paper, we fabricated a dual-photo-initiator photopolymer by doping EY (Eosin Yellow) molecules into a TI (Titanocene, Irgacure 784@BASF) dispersed PMMA (poly-[methyl methacrylate]) substrate system, with the aim of promoting the diffusion and polymerization processes in volume holographic storage. The two-wave interference system is adopted to record a permanent grating structure in our materials. The temporal diffraction variations of photopolymerization (during the interference exposure) and dark diffusion (after the interference exposure) processes have been investigated and analyzed. Aiming to analyze the influence of EY doping ratios on holographic performances, some key parameters were examined in the experiment. We first measured the temporal evolution of diffraction efficiency, then an exponential fitting was adopted to obtain the response time. Finally, the angular selectivity was evaluated by the Bragg condition after holographic recording. Also, the temporal evolution of each component is described by the nonlocal polymerization-driven diffusion model with a dual-photo-initiator composition, theoretically. Furthermore, we experimentally achieved the holographic grating enhancement in both the dark diffusion and photopolymerization processes by doping appropriate EY concentrations, respectively. This work provides a foundation for the acceptability of TI&EY/PMMA polymers in further holographic storage research.