Hydrothermal synthesis has afforded five divalent zinc coordination polymers containing 4-(4-carboxyphenyl)-2,2′:6′,2′′-terpyridine (HL₁) or its isomer 4-(4-carboxyphenyl)-2,2′:4′,4′′-terpyridine (HL₂), with or without the addition of auxiliary ligands, 1,3,5-benzenetricarboxylic acid (H₃btc) and 1,4-benzenedicarboxylic acid (H₂bdc). Their structures have been characterized by single crystal X-ray analyses and further characterized by infrared spectra, elemental analyses, powder X-ray diffraction, thermogravimetric analyses and photoluminescent spectra. Across this series, the π⋯π interactions have a dramatic impact on the self-assembly of these entanglement structures, in either case it can exert an important structure-directing role. In addition, the disposition of pyridine nitrogen atoms in ligands also plays a large role in structure direction in this system. Complex 1 is a 2D + 2D→3D inclined polycatenated coordination polymer based on the resulting array of 2D (6,3) layers constructed by 1D→2D π⋯π directed self-assembly. Complex 2 is assembled into a 3D framework by means of 1D + 1D→3D mutual interdigitation based on 1D→1D self-assembly driven by π⋯π stacking interactions. Complex 3 shows a 2D + 2D→3D interdigital network involving 2D + 2D→2D parallel interpenetrated and 2D + 2D→2D interdigital (4,4) layer motifs. Complex 4 displays a 2D + 2D→3D polythreaded framework based on a 2D (4,4) network comprised of alternating rings and rods. Complex 5 is a (3,4)-connected 3D framework with topology (4.8².10³)(4.8²). In comparison with covalently connected entanglements, such π⋯π directing self-assembly of entanglements are far less explored, especially, polycatenane based on 1D chain motifs and polythread based on 2D layer motifs are rarely reported. Furthermore, the luminescent properties of complexes 1–5 at room temperature have also been studied in detail herein.