Sharpening of optical spectra caused by commensurate growth of an organic adlayer on salt single crystals is reported. The structure is elucidated by atomic force microscopy and advanced potential energy calculations. Continued deposition or annealing induces a rearrangement of the molecular monolayer into 3D crystallites, demonstrating the crucial role of the Coulomb interaction with the substrate to form the unexpected commensurate structure.