Traditionally, X-ray powder diffraction has been a favoured method for studying chemical reactions in the solid state, but the increasing importance of energy-efficient synthesis methods for solids (e.g. sol-gel synthesis, mechanochemical synthesis) has led to the need for an analytical method not dependent on long-range structural periodicity. Multinuclear solid state nuclear magnetic resonance (NMR) represents a technique which is equally applicable to amorphous or crystalline solids, and is now used in increasing numbers of solid state studies. This paper briefly outlines the principles and practical details of this powerful technique and gives examples of its use in solid-state chemistry, particularly in very recent studies of mechanochemical synthesis of advanced sialon ceramics. The temperature at which these technically important silicon aluminium oxynitride compounds are formed can be significantly lowered by high-energy grinding of their components to produce X-ray amorphous precursors. Solid-state NMR has been Used to provide detailed information which could not have been obtained by any other means about the chemical environment of the Si and Al atoms in these amorphous precursors, and the various atomic movements undergone as they crystallise to the final product. (C) 2004 Elsevier B.V. All rights reserved.