A novel coordination polymer, namely, [Ca3(BIPA)3(H2O)3·H2O]n (1) has been prepared by the reaction of 5-bromoisophthalic acid (H2BIPA) with corresponding Ca(II) ions, and characterized by single-crystal X-ray diffraction, element analysis, infrared spectroscopy, thermogravimetric analysis In compound 1, a trimer unit [Ca3O19] is bridged the carboxylate oxygen atoms, forming an inorganic layer structure. The inorganic layers are linked by the BIPA2− ligands, resulting in a three-dimensional (3D) pillared layered structure with a binodal (4,9)-connected 3D net structure with Schlafi symbol of (34·42)(38·410·512·66). In compound 1, the carboxylate groups of the BIPA2− ligands coordinate to calcium ions using different coordinated modes. In addition, the thermal stability and luminescent properties of 1 were also investigated.