The study of complex organic, inorganic and composite systems is greatly facilitated by solid state nuclear magnetic resonance (NMR) spectroscopy. This is especially true for materials lacking crystalline long-range order or having low atomic mass contrast, such as amorphous organic materials, which renders other methods such as x-ray diffraction (XRD) and transmission electron microscopy (TEM) incapable of comprehensive characterization. In this dissertation, a variety of one- and two-dimensional (2D) solid-state NMR measurements are applied to investigate the composition and nanometer-scale structure of a variety of organic-inorganic hybrid systems as well as complex inorganic phases. Bone, which is a natural nanocomposite of an inorganic apatitic phosphate and the organic protein collagen, has been studied by 1H single-resonance, 1H-31P and 1H-13C double-resonance, as well as 1H-13C-31P triple-resonance experiments. Analysis of 31P dephasing by heteronuclear recoupling with dephasing by strong homonuclear interactions of protons (HARDSHIP) has provided information about the size of the apatite nanocrystals. The concentrations of various moieties in the composite, such as the OH-, CO32-,HPO4 2-,H2O-PO43-, and Na in the inorganic apatite, were determined by quantitative spectroscopy via spectral selection of specific chemical moieties. X{lcub} 1H{rcub} HARDSHIP NMR was used to prove their incorporation into the apatite nanocrystals. 31P chemical shift anisotropy (CSA) dephasing experiments as well as 1H{lcub}31P{rcub} rotational echo double resonance (REDOR) experiments have identified and quantified the hydrogen and phosphate species located at the surface and the interior of the apatite crystal. Strongly bound H2O, as well as a layer of viscous water, is present at the organic-inorganic interface, as proven by 1H spin-diffusion detected via 13C and 31P nuclei. Investigation of the proximity of organic moieties to the apatite surface via 13C{lcub}31P{rcub} heteronuclear recoupling experiments provide a structural insight of the organic-inorganic interface.;Biomimetic synthetic organic-inorganic phosphate hybrid materials have been investigated. 31P NMR spectroscopy has enabled identification and quantification of the different types of phosphates in these materials, and the formation of nanocomposites is proven by wideline separation (WISE) NMR with spin diffusion. A bone-replacement material, Si/Zn-doped beta-tricalcium phosphate (TCP), has also been investigated. Spectral selection techniques based on J-modulation and double-quantum filtering have enabled elucidation of the spectrally overlapping silicate Q species. 29Si{lcub} 31P{rcub} REDOR proves that while the silicate is indeed incorporated into the TCP matrix, it is significantly aggregated into ∼7 nm diameter domains. Further, a new class of hybrid systems based on polyamide 6 and phosphate glass was studied, where HARDSHIP has confirmed the formation of nanocomposites of the phosphate glass dispersed in the polyamide matrix. 1H- 31P heteronuclear correlation (HetCor) NMR indicated phosphate-polyamide interactions and alterations of the phosphate glass surface by the polyamide matrix. 13C NMR has also shown that the phosphate glass promotes the crystalline gamma-phase of the polyamide.