Abstract: Two novel metal-organic complexes Pb(cbba)₂(m-bix)_n(1) and Zn₂(btx)₂(NDC)_2n(2) (H₂cbba=2-(4-chlorobenzoyl)-benzoic acid, m-bix=1,3-bis(imidazol-1-ylmethyl)-benzene, btx=1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, H₂NDC=1,4-naphthalenedicarboxylic acid) have been hydrothermally synthesized. The structure was characterized by techniques of elemental analysis, infrared spectra, single-crystal X-ray diffraction analysis, powder X-ray diffraction. The results showed that the complex 1 is triclinic, space group of P−1, and the central Pb(Ⅱ) has a deformed tetrahedron configuration. The crystal cell parameters are a=1.13521(3) nm, b=1.19508(3) nm and c=1.42289(4) nm. However, the complex 2 is monoclinic, space group of I2/m, and the central Zn(Ⅱ) has a tetrahedron configuration. The crystal cell parameters are a=1.99118(6) nm, b=2.11760(4) nm and c=2.77804(8) nm. The complex 1 exhibited 0D structure, which extended into a 3D 6-connected supramolecular network by means of abundant non-classical C−H∙∙∙O and C−H∙∙∙Cl hydrogen bonding forces, and the point symbol of this network is 4¹².6³. While the complex 2 featured a double Zn(Ⅱ) 1D chain with the symbol of 4².6, which extended into a 3D 6-connected supramolecular network by means of abundant non-classical C−H∙∙∙O and C−H∙∙∙Cl hydrogen bonding forces. In addition, photoluminescence investigations revealed that complex 1 has green emission at 519 nm and 555 nm respectively, while complex 2 has purple and blue emission at 392 nm and 463 nm respectively, indicating that both of the complexes can be used as potential fluorescent materials.