A novel 3D entangled ZnII-coordination polymer {[Zn(abtc)0.5(btb)]·2H2O} n (1) [H4abtc = 3,3′,5,5′-azobenzenetetracarboxylic acid, btb = 1,4-bis(1,2,4-triazol-1-yl)butane] was synthesized under hydrothermal reaction conditions and characterized by elemental analysis, IR spectra, TG, PXRD and single-crystal X-ray diffraction. In compound 1, the μ4-abtc4− tectons act as the square-planar nodes to link the ZnII ions into 2D helical layers, while the secondary btb ligands further connect tetrahedral [ZnO2N2] building units into 2D motifs, resulting in a (4,4)-connected self-penetrating 86 binodal networks that can be viewed as cross-linking of two interpenetrating (3,4)-connected networks. The thermal stability and photoluminescence property of 1 were also investigated. Synthesis, structure and spectroscopic characterization of a novel (4,4)-connected self-penetrating 86 binodal coordination network. A novel 3D self-penetrating 86 binodal networks, with mixed tetrahedral and square-planar nodes, have been successfully constructed by two type of btb ligands interconnecting meso-helical [Zn2-abtc] n layers, which can be viewed as cross-linking of two interpenetrating (3,4)-connected networks. The thermogravimetric analysis and the photoluminescence properties of complex 1 were also studied.