In the title compound, [Ni(C12H6O4)(C22H16N2O)2(H2O)2]n, the Ni(2+) cation resides on a centre of inversion in a slightly distorted octahedral [N2O4] environment. The two carboxylate groups of each naphthalene-2,6-dicarboxylate (NDC(2-)) ligand, which reside on centres of inversion, link the Ni(II) cations into a one-dimensional chain. Identical chains are linked by intermolecular hydrogen bonds between coordinated water molecules and the uncoordinated N atoms of 4-{4-[4-(pyridin-4-yl)phenoxy]phenyl}pyridine ligands to form (4,4)-topological sheets, and then the different sheets are interlocked in an inclined fashion to give a three-dimensional polycatenation network. The stability of the structure is further enhanced by π-π stacking interactions between pyridine and benzene rings.