To understand amorphous and structurally disordered materials requires the application of a wide-range of advanced physical probe techniques and herein a combined methodology is outlined. The relatively short-range structural sensitivity of solid state NMR means that it is a core probe technique for characterizing such materials. The aspects of the solid state NMR contribution are emphasized here with examples given from a number of systems, with especial emphasis on the information available from 17O NMR in oxygen-containing materials. 17O NMR data for crystallization of pure sol-gel prepared oxides is compared, with new data presented from In2O3 and Sc2O3. Sol-gel formed oxide mixtures containing silica have been widely studied, but again the role and effect of the other added oxide varies widely. In a ternary ZrO2-TiO2-SiO2 silicate sol-gel the level of Q4 formation is dependent not only on the composition, as expected, but also the nature of the second added oxide. Sol-gel formed phosphates have been much less widely studied than silicates and some 31P NMR data from xerogel, sonogel and melt-quench glasses of the same composition are compared. The effect of small amounts of added antibacterial copper on phosphate glass networks is also explored.