Perylene diimides (PDIs) substituted with a terpyridine moiety at the bay-region have been synthesized. These building blocks were used to construct supramolecular complexes in chloroform. A dimer and a trimer were built via the bay-region complexation with zinc. The PDI compounds were further modified to have silane anchors and PDI self-assembled monolayers (SAMs) were prepared on a quartz substrate. Complexation of metal ions was also done on the surface, and this was observed clearly in the absorption spectrum. These studies on the surface show possible progress in the study of supramolecular multilayer structures.