NMR diffusion measurements on 10 different multicomponent hydrogen-bonded assemblies, viz. the three single rosettes SR1–SR3 ( 13· 2a3, 13· 2b3, 13· 2c3) the double rosettes DR1–DR5 ( 3a3· 2a6, 3b3· 2b6, 3c3· 2a6, 3d3· 2a6, 3e3· 2a6), and DR6 ( 4a3· 16), and the tetrarosette TR ( 53· 2a12) are described. Some of the above rosettes have been previously identified as well-defined assemblies (viz. SR1, DR1–DR3, and TR) using established characterization techniques (1H NMR spectroscopy, X-ray diffraction, and MALDI-TOF MS after Ag+-labeling). The diffusion coefficients of these assemblies were studied and used as a reference for the identification of three new assemblies ( DR4–DR6), the characterization of which could not be established unequivocally using other characterization tools. A good correlation was found between the experimental and calculated diffusion coefficients when DR1 was used as a reference. A relatively good correlation was obtained between the effective hydrolytic radii calculated from the diffusion data and those extracted from gas phase-minimized structures with SR1 and DR2 being exceptions. The diffusion measurements show that assembly DR4 is a thermodynamically stable species, while assemblies DR5 and DR6 are less stable and only present to a minor extent.