Two new types of phenanthrenequinone-doped poly(methyl-methacrylate) (PQ/PMMA) are proposed and fabricated for volume holographic recording. In these materials, the matrix of PQ/PMMA is replaced by the copolymers, which are composed of either poly(trimethylolpropane triacrylate-co-methyl methacrylate) or poly(2-phenoxyethyl acrylate-co-methyl methacrylate), respectively. With the chemical analyses of the response of these materials with respect to light exposure, the physical mechanism of the holographic recording in those copolymer samples is investigated. In addition, the holographic characteristics, including the dynamic range and sensitivity, have been measured. The experimental results demonstrate that the modification of the monomer components can enhance holographic characteristics of PQ/PMMA.