A series of zinc(II) coordination polymers with 5-methoxyisophthalate (CH3O–H2ip) and five related flexible N-donor ancillary ligands, [Zn(CH3O-ip)(bime)0.5] (1), [Zn(CH3O-ip)(btx)]2·H2O (2), [Zn(CH3O-ip)(bix)]2 (3), Zn(CH3O-ip)(bib) (4), [Zn2(CH3O-ip)2(bbim)]2 (5) [bime = 1,2-bis(imidazol-1′-yl)ethane, btx = 1,4-bis(triazol-1-ylmethyl)benzene), bix = 1,4-bis(imidazol-1-ylmethyl)benzene, bib = 1,4-bis(2-methyl-imidazol-1-yl)butane, bbim = 1,1′-(1,4-butanediyl)bis(benzimidazole)], have been synthesized under hydrothermal conditions. Complexes 1–5 were structurally characterized by elemental analysis, infrared spectra and X-ray single-crystal diffraction. These complexes display different types of entanglements. Complex 1 features an extended 3D polythreaded network based on 2D coordination frameworks with a (3,4)-connected (42.6)(42.63.8) topology. Complex 2 shows a rare example of entangled coordination polymer containing both interpenetrating and polythreading features. Complex 3 manifests a highly corrugated 2D (4,4) layer. The layers are penetrated by each other to give rise to 3D polycatenations. While 4 and 5 exhibit three-fold interpenetrated 3D 4-connected (65.8) and (3,4)-connected (42.6)(184.108.40.206) topologies, respectively. These results suggest that both 5-methoxyisophthalate and N-donor ancillary ligands influence on the final resulting structures. Furthermore, luminescent properties and thermogravimetric properties of these complexes were investigated.