A series of highly luminescent-active metal-organic frameworks (MOFs) 1-3 with hierarchical pores have been rationally constructed and fully characterized. The predesigned semi-rigid hexacarboxylate ligand hexa[4-(carboxyphenyl)oxamethyl]-3-oxapentane acid (H6L) has been adapted with various space-directed Ndonors (i.e., 2,2'-bipyridine, 4,4-di(1H-imidazol-1-yl)-1,1-biphenyl, and 1,3,5-tri(1H-imidazol-1-yl)benzene) from a bidentate V-shape to a tridentate Y-shape. This family of multifunctional MOF materials represents a variety of potential applications in the following aspects: first, as luminescent sensors that show a fast and sensitive detection for pollutant CrO42- and Cr2O72- ions in aqueous media; second, as adsorbents that can rapidly remove harmful organic dyes; third, as an antenna that can effectively sensitize visible-light-emitting Tb3+ ions. These multifunctional MOF materials combine optical-sensing, adsorption, and sensitization properties, thus are very useful in many potential applications. Furthermore, these materials have proved to be reusable.