On edge: Self‐assembled monolayers of a bis(hydrazone)‐based molecular grid physisorbed on graphite are studied by scanning tunneling microscopy (see picture). High order is attained at the supramolecular level by thermal annealing of the grid‐based films. A preferential edge‐on configuration of the molecular grid with respect to the substrate is found. Self‐assembly of a bis(hydrazone) chelating ligand functionalized with octadecyloxy substituents is described, as well as the reproducible thermally activated self‐assembly of its metallosupramolecular cationic CoII [2×2] grid‐type complex, on a highly oriented pyrolitic graphite (HOPG) substrate. Scanning tunnelling microscopy measurements at the solid/liquid interface reveal that the grid units of the annealed films are oriented edge‐on to the basal plane of the HOPG, which indicates that the influence of the octadecyl chains is not sufficient to tie the grids …