The photoproducts in phenanthrenequinone (PQ)-dissolved methyl methacrylate (MMA) liquid samples and PQ-doped poly(methyl methacrylate) (PQ/PMMA) solid photopolymer samples have been analyzed by various chemical measurements. A mechanism for holographic recording in our PQ/PMMA photopolymer is proposed. By UV-VIS transmission and photoluminescence spectral measurements, we find that under light exposure the molecular structure of PQ is transformed to be less conjugated. The measured results of mass spectra, Fourier transform infrared spectra, NMR spectra, and gel permeation chromatograph analyses provide some evidence for recognizing the molecular structure of the photoproducts in our PQ/PMMA photopolymers. The results show that under light exposure the PQ and MMA form new molecules, mainly an adduct of one PQ molecule with one MMA molecule. In addition, PQ also reacts as a photoinitiator to form PMMA oligomers in our samples. The structure change of the PQ molecule induces a strong change of the refractive index in the material. It provides a mechanism to record a phase hologram in our PQ/PMMA photopolymer. Holographic recordings in the samples are demonstrated, and the dynamic range of the sample is investigated. © 2004 Society of Photo-Optical Instrumentation Engineers.