A new inorganic–organic hybrid lead(II) coordination polymer [PbCl(tza)] n (Htza=tetrazole-1-acetic acid) has been synthesized under hydrothermal condition. The complex was characterized by elemental analysis, FT-IR spectroscopy, single-crystal X-ray analysis, thermogravimetric analysis (TG) and differential scanning calorimetry thermal analysis (DSC). The Pb(II) centers are connected through both the tza and Cl − bridging ligands to form a three-dimensional metal–organic framework (MOF). The compound has been found to exhibit blue photoluminescence in the solid state at room temperature and may be good candidates for photoactive materials. DSC thermal analysis shows the complex is an energetic coordination compound and tza can be used as an energetic ligand.