Solid-state nuclear magnetic resonance (ssNMR) is a versatile technique that can provide structural information on complex materials in functionally-relevant states. An emerging area of ssNMR research concerns the extracellular matrix (ECM), a class of highly diverse biological materials composed of a heterogeneous mixture of molecular entities, including proteins, glycans, glycoproteins, and other biomolecules. These molecules show specific interactions and organisation at a range of length scales. SsNMR can contribute structural insight at the atomic length scale, potentially on ECM and ex vivo tissues samples with minimal processing or purification.