NMR spectroscopy is the key analytical method for determination of chemical structure and investigation of physico-chemical properties, such as non-covalent interactions, tautomeric equilibria or polymorphism. In this work, selected examples of using advanced NMR methods in structural analysis are discussed. (1) NMR spectroscopy with in situ irradiation useful to monitor photochemical processes, (2) 31P NMR spectroscopy for reaction monitoring and probing stereochemistry and (3) solid-state NMR spectroscopy to investigate polymorphism.