In this tutorial review we intend to give an overview of the potential of NMR spectroscopy, and in particular solid-state NMR, in characterising micelle-templated mesoporous materials. Different topics are covered including the study of formation mechanisms, the characterisation of structures, textures, surfaces and interfaces, functionalisation, dynamic properties and structure–reactivity correlations. Some selected examples illustrate the variety of information provided by this spectroscopy. Particular attention is paid to recent technological and/or methodological developments.