Secondary ion mass spectrometry (SIMS) is an analytical technique that can be used to characterise the surface and near-surface region of solids. The instrument operation and data analysis have been discussed to obtain meaningful results. The paper discusses the technique of sequential sputtering to elucidate the thickness of individual layers in a multilayer structure. The application of the technique for failure analysis, standard generation and interface studies have been discussed in detail taking examples of multilayer structures of compound semiconductors being developed at SSPL.