Four new ZnII-coordination polymers (CPs), namely [Zn3(4-bmbpd)2(1,4-BDC)3] (1), [Zn(4-bmbpd)(4,4′-OBA)]·H2O (2), [Zn3(4-bmbpd)1.5(2,2′-BDC)3] (3) and [Zn(4-bmbpd)(1,3,5-HBTC)]·2H2O (4) (4-bmbpd = N,N′-bis(4-methylenepyridin-4-yl)-1,4-benzenedicarboxamide, 1,4-benzenedicarboxylic acid (1,4-H2BDC), 4,4′-oxybisbenzoic acid (4,4′-H2OBA), 2,2′-biphenyldicarboxylic acid (2,2′-H2BDC) and 1,3,5-benzenetricarboxylic acid (1,3,5-H3BTC)), have been synthesized with ZnII ions and the 4-bmbpd ligand in the presence of auxiliary polycarboxylate ligands under hydrothermal conditions and have been fully structurally characterized by single-crystal X-ray diffraction analyses, thermal gravimetric analyses (TG), IR spectroscopy and powder X-ray diffraction (PXRD). The structural analysis reveals that complexes 1–3 are all 2D networks with different structural details adjusted by the different polycarboxylate ligands. Complex 4 is a 3D threefold interpenetrated framework with an uncoordinated carboxyl group. The effect of the polycarboxylate ligands on the structures of the title complexes is discussed. The solid-state fluorescent properties of the title complexes have been determined at room temperature. The title complexes exhibited good selectivity for the luminescent detection of Fe3+ ions in aqueous solution with mixed metal ions, which make them promising crystalline materials as luminescent probes for the Fe3+ ion.