We demonstrate volume holographic recording at a wavelength of 640 nm in a photopolymerizable nanoparticle-polymer composite (NPC) film dispersed with ultrahigh refractive index hyperbranched-polymer (HBP) organic nanoparticles. We employ a new photosensitizer-initiator system consisting of cyanine dye, triazine compound and borate salt for efficient radical generation in the red. We investigate the electron transfer and radical generation processes of the system by measuring fluorescence quenching and photopolymerization dynamics to find the optimum composition of the system for volume holographic recording. We show that recorded volume gratings of 0.5-µm spacing possess the saturated peak-to-mean refractive index modulation amplitudes as large as 3×10⁻² at a readout wavelength of 640 nm. Our results show the usefulness of photopolymerizable HBP-dispersed NPCs for volume holographic recording materials for various photonic applications including security and color holograms, and volume Bragg grating devices in head-mounted displays.