Spherical particles with well-defined diameters were obtained by self-assembly of trityl-based molecules. Thanks to the robustness of the organic scaffold, a variety of modifications could be covalently introduced into the network so as to stabilize the supramolecular structure by a sol-gel route. Using supramolecular chemistry, we showed that the synthesis of hybrid small molecules allowed engineering nanomaterials with tunable size and functionality. The use of a combination of différent characterization techniques, including dynamic light scat-tering, cryoTEM, and solid-state NMR spectroscopy, providedcareful understanding of the relationship between the molec-ular and supramolecular structures for further chemical engineering of supramolecular hybrid materials.