A Ce:YAG-poly(methyl methacrylate) composite was prepared using in situ polymerization by embedding the Ce:YAG nanopowder in a blend of methyl methacrylate (MMA) and 2-methacrylic acid (MAA) monomers and activating the photopolymerization using a radical initiator. The obtained nanocomposite was yellow and transparent. Its characterization was performed using transmission electron microscopy, small angle X-ray scattering, (13)C cross-polarization magic-angle spinning nuclear magnetic resonance, and photoluminescence spectroscopy. Results showed that Ce:YAG nanoparticles are well dispersed in the polymeric matrix whose structure is organized in a lamellar shape. The luminescence properties of the nanocomposite do not show quenching or a significant spectral shift, indicating that the nanocomposite can be useful for advanced applications such as white LED construction.