Two new complexes based on the aromatic ligand [2-(4'-pyridyl)-benzoxazole] (4-PBO), Ag(4-PBO)(2)NO3 (I) and MnCl2(4-PBO)(2)(H2O)(2) (II), are presented. Complex (I) is a wavelike supramolecular layer structure assembled by pi center dot center dot center dot pi stacking interaction, and complex (II) is a three-dimensional supramolecular framework structure assembled by pi center dot center dot center dot pi stacking and hydrogen bonding interactions. The electronic absorption and photoluminescence characterizations for complex (I) and thermal stability properties for both complexes have also been studied on as-synthesized powder samples.