Metal–organic frameworks (MOFs) and covalent-organic frameworks (COFs) are materials typically featuring ordered long-range structures and permanent porosities, which have many promising potential applications. Solid state nuclear magnetic resonance (SSNMR) provides rich molecular-level information that is exceptionally useful for the structural characterization of MOFs and COFs. In this chapter, we summarize the history of MOFs and COFs, provide a general background of NMR concepts and describe some typical SSNMR experimental approaches. The three primary types of structural information obtainable from MOFs and COFs using SSNMR spectroscopy are then detailed, and the chapter concludes with an outline of key points presented in the remainder of this book.