Glasses remain a focus of attraction to fundamental researchers and materials engineers alike. The desire of controlling physical property combinations by compositional design inspires the search for fundamental structural concepts describing the short- and medium-range order of the glassy state. From its early beginnings more than 60 years ago, solid-state nuclear magnetic resonance (NMR) spectroscopy has been making significant contributions toward this objective. Being element-selective, inherently quantitative as well as selective to the local environment, NMR in many ways presents an ideal experimental tool of structural investigation of glasses. Over the years, substantial NMR methods development, along with advances in the theoretical interpretation of NMR parameters, have significantly enhanced our fundamental knowledge of medium-range order and of composition-structure-function relationships. This article takes a look back at the amazing scientific trajectory this field of investigation has taken, from the early beginnings to the present state of the art. As such, this overview does not strive to be comprehensive, but adopts a personal perspective, highlighting what in the view of the author have been influential developments and important insights obtained during the various phases of scientific inquiry in this research field.
