Photopolymers hold great promise for the preparation of transparent volume holographic gratings (VHG), which are core optical elements in many application fields. To improve the holographic recording property of a two-stage photopolymer, four new (meth)acrylate monomers (CTA, CTMA, CTBA, CTBMA) with high refractive indices (1.59−1.63) are designed and synthesized in this study. Using them as one writing monomer, a series of photopolymer samples with different formulations and thicknesses are fabricated for holographic recording. Among them, a formulation containing 9 wt % CTMA shows the best performance. Using it as a recording medium, a VHG with high resolution and diffraction efficiency is constructed. Its refractive index modulation reaches 0.046. Moreover, its total transmittance within 400−800 nm achieves 96.62% after photobleaching. The results indicate that the CTMA-based formulation has great application potential in developing highperformance transparent VHG.