Reaction of the preorganized strands of {[Cu-II(mu-4,4'-bpy)](2+)}(n) (4,4'-bpy = 4,4'-bipyridine) with [W-V(CN)(8)](3-) leads to a novel cyano-bridged (Cu3W2V)-W-II complex [Cu(mu-4,4'-bpy)(DMF)(2)][Cu(mu-4,4'-bpy)(DMF)](2)[W-V(CN)(8)](2).2DMF.2 H(2)O 1. The structure of 1 consists of the expected 2-dimensional grid-type network which is built of infinite {[Cu-II(mu-4,4'-bpy)](2+)}(n) chains cross-linked by octacyano-tungstate units. The Cu-II-NC-W-V-CN-Cu-II linkage exhibits the topology of a 3,2-chain. The skeleton of the layer is additionally stabilized by a hydrogen bond network formed by terminal cyano ligands of the [W(CN)(8)](3-) moiety and water molecules. The distance between the adjacent (Cu3W2V)-W-II chains within the layer is 11.12 Angstrom along the a axis. The layers are connected by H-bonds of NCN-NDMF-NCN linkages into 3-D supramolecular architecture. The magnetic properties correspond to a dominant ferromagnetic coupling within the (Cu3W2V)-W-II pentamer units (J = +35(4) cm(-1)) and much weaker effective AF interunit coupling which include both intra- and inter-3,2-chain interactions between pentamers (J = -0.05(1) cm(-1)).