Diamondoids are a group of diamond-like hydrocarbon cage molecules that have emerged as promising candidates in a wide range of applications. For example, the inherent properties of diamondoids allow for their application as scaffolds in nanotechnology. Following that rationale, we recently prepared diamondoid ether molecules with a goal to study their self-organization on a highly oriented pyrolytic graphite (HOPG) surface.[1, 2] The deposited diamondoid ethers formed ordered monolayers which were structurally characterized using scanning tunneling microscopy. We also conducted a detailed computational analysis that revealed the most favorable on-surface orientations of these rigid molecules (Figure 1) and confirmed that their spontaneous self-assembly was governed by London dispersion interactions acting between cage subunits. We also found that the oxygen atom played an important role in directing the molecules towards the graphite surface, whereas the abundant side C–H contacts between the cages were crucial for the formation of an ordered 2D lattice.