To be or not to be chlorinated: When octaethylporphyrin iron(III) chloride (FeOEPCl) molecules are sublimated onto Cu(111) surfaces, two different molecular species are observed through scanning tunneling microscopy, showing either a protrusion or a depression at the center. In combination with van der Waals‐corrected density functional calculations, our experiments reveal that one species corresponds to FeOEPCl molecules with the chlorine atom pointing away from the surface, whereas the other species has been dechlorinated.