Two new compounds [Zn 2 L(OH)H 2 O] n (1) and [Cd(HL)] n (2) have been assembled from a semirigid V-shape ligand under hydrothermal conditions. The two compounds were determined by single-crystal X-ray diffraction analyses and further characterized by solid state emission spectra, IR spectra, and thermogravimetric analyses. Single crystal X-ray diffraction analyses show that both of the two compounds crystallize in space group P1¯ and display a three-dimensional (3D) structure with different topologies of fluorite topology for 1 and Au 4 Ho topology for 2. It is noteworthing that 1 has a novel Zn 2 dinuclear unit containing only one bridging oxygen atom between two Zn atoms. Studies of photophysical properties reveal that 1 and 2 present luminescence, which can be ascribed to the emission of intraligand transition.