Chaperone–client interactions are highly dynamic in their nature and result in transient, multi-conformational complexes that are challenging to characterize at the atomic level. Solution NMR spectroscopy has the power to resolve structure and dynamics even for large molecular systems in aqueous solution and is therefore a method of choice for chaperone–client systems. Here, we categorize the NMR techniques suitable for the characterization of dynamic complexes, assess their particular usefulness for chaperone–client complexes and describe how the resulting data can be fruitfully interpreted toward structural models.