Holographic optical waveguide is the most practical waveguide coupling technology for head-mounted augmented reality displays (HMD-AR) due to its advantages of small size, lightweight, clear imaging, flexible design, and a large eye-movement range for users. To enhance the imaging capability of the HMD-AR system and expand its field of view, the volume holographic gratings (VHG) used as the coupling-in and coupling-out elements must have a high refractive index modulation (Δn). Photopolymer is one of the most promising recording media for manufacturing high-performance transparent VHG. The working principle of holographic optical waveguide in HMD-AR and the preparation principle of photopolymer VHG are introduced, the recent research progress of photopolymers in this field is reviewed, the influence of different components in photopolymer formulations and the post-treatment methods of the recording media on their holographic optical properties are summarized, mainly including: (1) the composition of the photoinitiator systems; (2) the crosslink density, molecular weight and refractive index of the film-forming resins; (3) the refractive index, addition and size of the writing monomers; (4) the additive of nanoparticles, chain transfer agents, free radical scavengers and plasticisers; (5) post-treatment methods such as heating and/or light. It is expected to provide guidance for designing new components, developing recording media with higher Δn, and fabricating HMD-AR with better performance.