Intercalation of surfactant and polymer chains between the clay platelets gives rise to molecular ordering that changes both the chain conformation and mobility with respect to the bulk phase. As a local probe, nuclear magnetic resonance is particularly suited for such investigations, and this review reports the main results obtained in the solid state. The properties of the modified clays are studied as a function of the surfactant loading, the nature of the head group, and the length of the hydrocarbon chain(s). The structure and charge of the mineral also influence the behaviour of molecules in the gallery space. Among papers on polymer/clay nanocomposites, those dealing with poly(ethylene oxide) have been studied in particular, using a multinuclear approach. Natural clays often contain paramagnetic species such as Fe(III) that perturb the nuclear magnetic resonance (NMR) relaxation processes and can prevent observation of appropriate NMR data. Accordingly, most organic/clay hybrids are studied with hectorite or synthetic smectites. However, the paramagnetic effect has also been found useful in characterizing clay dispersion within the polymer matrix of the nanocomposites.