Hierarchical self-assembly of 13-cis-retinoic acid on Au(111) and Ag(111) was investigated using low-temperature scanning tunnelling microscopy. On both surfaces, molecules form dimers by hydrogen bonds and the dimers arrange into ordered two-dimensional arrays through van der Waals forces. Three packing modes are observed on Au(111) and only one on Ag(111). We tentatively attribute the different patterns on the two surfaces to a stronger molecule–substrate interaction on Ag(111) and site-dependent molecular adsorption on different atomic lattices. In addition, 13-cis-ReA on Au(111) can be made to carry a localized spin.