Presented here is a new heterometallic coordination polymer, namely [ZnCa(btec)(H2O)2]n (1 H4btec = 1,2,4,5-benzenetetracarboxylic acid), which was successfully synthesized via the hydrothermal reactions of H4btec, Zn(NO3)2 and CaCl2. Single crystal X-ray structural analysis reveals that compound 1 features a 3D inorganic–organic hybrid framework, which can be simplified into a (4,8)-connected scu topological network by viewing Zn(II) ions, Ca(II) ions, btec4− ligands as 4-, 4-, and 8-connected nodes, respectively. Moreover, the luminescent properties of compound 1 and the desolvated samples were also investigated at room temperature.