A dicyanoamide-bridged 2D polynuclear zinc(II) complex having formula [Zn2(L)(µ-dca-KN1 KN5)2] n, 1 has been synthesized using the Schiff base ligand N,N'-bis(salicylidene)-1,3-diaminopentane, (H2L) and sodium dicyanoamide [Na(dca)]. The complex presents a 2D hexagonal structure formed by 1,5-dca singly bridged helical chains connected through double 1,5-dca bridges. The ligand and the complex are well characterized by elemental analyses, IR and UVvis spectroscopy. Thermogravimetric analysis is performed to investigate the thermal stability of the metalorganic framework. Photoluminescence studies of the Schiff base ligand in methanol and of the zinc(II) complex 1 in solid state show the presence of blue emission. The emission of the ligand occurs from an excited state involving an intramolecular proton-transfer process as a result of ketoenol tautomerisation and the zinc(II) complex emits from a ligand-centered excited state. © 2011 The Chemical Society of Japan.