The zinc complexes, [Zn(OS(O)2Me)2(H2O)2]n1 and [Zn(OS(O)2Me)2(H2O)4]n2 are obtained as hydrolysis products of the homoleptic zincate salt, [Et4N]2[Zn(OS(O)2Me)4]. The reaction of 2 with 4,4′-bipyridine (4,4′-bipy) in dry methanol yields [{Zn(4,4′-bipy)(H2O)4}(OS(O)2Me)2]n, 3. The structure of 1 adopts one-dimensional polymeric motif by virtue of bridging bidentate mode of methanesulfonate groups while 2 is a molecular entity with monodentate sulfonate groups directly bonded to the zinc atom. The coordination framework of 3 is composed of infinite arrays of cationic [ZnO4N2] octahedra with methanesulfonate anions being located in the secondary coordination sphere. The sulfonate group in 1–3 acts as a hub for O–H…O type hydrogen bonds and assists the formation of two-/three-dimensional supramolecular assemblies.