In this review, we present applications of NMR spectroscopy as a potent tool for the study of molecular interactions. It is clear that a variety of NMR methods may be employed to deduce key features of ligand–receptor molecular recognition processes, looking at the process from the perspective of the receptor or the ligand. We have not provided an exhaustive review, but we have tried to focus on describing the different aspects within this research topic. We have therefore selected examples accordingly, depending on the particular problem under study or the application/development of protocols to circumvent the technical problems that may be found when working in this field.