Today the capability to rationally design and construct hybrid materials utilizing a performance-property driven methodology is strongly dependent on our ability to control the structure and the dynamics of hybrid interfaces. This control needs a deep knowledge of their molecular and supramolecular dynamics that must be evaluated in situ, in the soft matter or colloidal states. For this purpose the use of modern methodologies of characterization such as time resolved synchrotron experiments and advanced pulsed field gradient NMR methods (DOSY) is particularly relevant. In this critical review, two important examples are discussed. They concern, first, the study of surface capping organic components' affinity towards nanoparticle surfaces by DOSY NMR. The knowledge and therefore the tuning of this affinity is paramount because it controls solubility, transferability and stability of colloidal dispersions of nanoparticles (NPs). In the second part, the mechanism of micellar templated formation of hybrid mesophases will be discussed in the frame of the main results obtained via in situ SAXS (107 references).