A silica-poly(methyl methacrylate) (PMMA) composite was prepared by condensation polymerization of a 2 nm shell of the silane coupling agent 3-(trimethoxysilyl)propyl methacrylate (TPM) on the surface of 10.5 nm diameter sol-gel colloidal silica particles followed by free-radical polymerization of a 50 wt % dispersion of the TPM-silica in methyl methacrylate. Cross-polarization combined with magic angle spinning and high-power decoupling (CP/MAS) and single-pulse Si-29 NMR spectra together with quasi-adiabatic cross-polarization (QACP) C-13 NMR spectra provided quantitative analyses of the structural components of the parent silica, the TPM-silica, and the composite. The parent silica contained one ethoxy group and eleven hydroxy groups per ten silicon atoms. The TPM-silica contained one residual methoxy group per TPM group and no residual hydroxy groups. Polymerization with MMA consumed 85% of the methacrylate groups of the TPM. Time constants T-1 rho H for proton spin-lattice relaxation in the rotating frame detected via C-13 and Si-29 CPMAS spectra showed rapid spin diffusion between all CH protons in the samples, but not between the CH protons and the OH protons that cross-polarize Si-29 atoms in the parent silica. Time constants T-1 rho C for carbon spin-lattice relaxation in the rotating frame showed that the TPM-silica has substantial motion at kilohertz frequencies leading to fast relaxation, whereas the PMMA composite is more rigid and the ethoxy groups in the parent silica are more mobile. Measurements of H-1-H-1 dipolar transverse relaxation times via C-13 and Si-29 detection showed decreasing strengths of homonuclear dipolar interactions due to increasing molecular motion in the order composite > TPM-silica > OH groups in parent silica.