The nuclear magnetic resonance (NMR) properties of a smectite clay low in paramagnetic ions, and NMR experiments to detect organic material near the silicate surfaces with high sensitivity, have been explored by 1H, 29Si, and 13C NMR. In oven-dried hectorite clay, 1H NMR reveals a sharp signal at 0.35 ppm that narrows significantly with spinning speed. It is assigned to the "inner" OH protons of the silicate layers. In fluorohectorite, where the OH groups are replaced by fluorines, no such 1H peak is observed. The assignment is further confirmed by the efficient cross-polarization observed in two-dimensional (2D) 1H-29Si HETCOR spectra, and by 29Si-detected REDOR experiments with 1H-dephasing in the 29Si dipolar field, which yield a 1H-29Si distance of 2.9 + 0.4 A. In these 1H-29Si experiments, the sensitivity of the 29Si signal is enhanced at least fivefold by refocusing the decay resulting from the inhomogeneous broadening of the single 29Si peak, stretching the 29Si signal out over 80 ms. The small 1H linewidth of this signal at spinning frequencies exceeding 4 kHz is attributed to the large proton-proton distances in the clay. The upfield isotropic chemical shift of the OH groups is explained by their inaccessibility to hydrogen-bonding partners, as a result of their location in hexagonal "cavities" of the clay structure. The well-resolved, easily selectable OH-proton signal and the high-sensitivity 29Si detection open excellent perspectives for NMR studies of composites of clays with organic molecules. Two-dimensional 1H-29Si and 1H-1H chemical-shift correlation experiments enable efficient detection of the 1H spectrum of organic segments near the clay surface. Combined with 1H spin diffusion, the organic segments at up to several nanometers from the clay surfaces can be probed. A 2D 1H-13C correlation experiment yields the 13C spectrum of the organic species near the clay surfaces. A mobility gradient of intercalated poly(ethylene oxide), PEO, segments is proven in 1H-3Si WISE experiments with spin diffusion.