A new layered zirconium phosphate parallel to Co(dien)(2)parallel to[Zr4H8P5O26]center dot 3H(2)O (denoted ZrPO-CJ37) has been synthesized hydrothermally by using a racemic mixture of a chiral cobaltammine complex Co(dien)(2)Cl-3 as the template. Its structure is determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, inductively coupled plasma, thermogravimetric, UV-vis, and photoluminescence analyses. The inorganic layer of ZrPO-CJ37 is built up from the linkage of Zr-centered octahedra and P-centered tetrahedra via vertex oxygen atoms forming a 4.6-net sheet. Its structure features the edge-sharing chains of Zr(OM)(6) (M = P, H) octahedra. The cobaltammine complex cations are located in the interlayer region and interact with the host network through H bonds. ZrPO-CJ37 exhibits interesting photoluminescence in the UV-vis spectral region. The edge-sharing chains of Zr(OM)(6) octahedra in the inorganic layer might be responsible for this unusual photoluminescence.