Diamondoids are natural polycyclic cage hydrocarbons with a structure resembling the diamond crystal lattice. Despite being structurally similar to diamond, diamondoids have a marked advantage over it since they can be selectively functionalized, making them applicable in areas ranging from medicine to nanotechnology. As part of our ongoing research, we synthesized diamondoid ether derivatives differing in the type, size and number of their cage subunits. Conducted STM/AFM measurements demonstrated the organization of diamondoid ether molecules on a graphite substrate (HOPG) and revealed the existence of self-assembled 2D layers. Comparing these 2D assemblies with crystal structures obtained from single-crystal XRD experiments and with computed models, we could ascertain London dispersion as a driving force for self- organization of such bulky molecules on a HOPG carrier surface.