A major research field in mechanistic systems biology is represented by the development of methods for investigating the structural and dynamic features of systems with multiple interacting components, in order to understand their function. A combination of NMR techniques can be used in such respect, among which the employment of paramagnetic metal ions, 13 C direct detection, and solid-state NMR, possibly supported by other techniques like small angle X-ray scattering. Among the results, the information on the conformational heterogeneity experienced by multicomponent systems in solution can be mentioned. The structural and functional characterization of large biological systems, not affordable with standard solution NMR techniques, can be tackled through a synergistic use of solution and MAS solid-state NMR. 13 C direct detection NMR spectroscopy is on the other hand advantageous for improving the quality and quantity of observed nuclear signals, for their intrinsically smaller linewidths and larger signal breadth. Details on these approaches are reviewed here.