Five new materials built from polyoxotungstates and Cu(II) ions as linkers have been synthesized by hydrothermal reactions from a mixture of sodium tungstate, copper chloride and bipyridine. The value of the initial pH, the nature of the heteroelement (P or Si) and of the ligand (2,2′- and/or 4,4′-bipyridine) permit the control of the nature of the polyoxotungstate clusters and their connectivity via the copper ions, and hence the dimensionality of the framework. A single phase has been obtained with silicon as heteroelement at an initial pH of 5, namely the 2D material [SiW12O40][Cu(2,2′-bpy)2]2·10H2O (1) with saturated Keggin polyoxotungstates linked by {Cu(2,2′-bpy)2}2+ groups. With phosphorous as heteroelement and at the same initial pH, three different structures have been isolated according to the nature of the ligand. Indeed, the two 1D materials [{Cu5(2,2′-bpy)5(H2O)(HPO4)(PO4)}PW11CuO39]·6H2O (2) with 2,2′-bpy and [4,4′-Hbpy][{Cu2(2,2′-bpy)2(4,4′-bpy)2.5}PW11CuO39]·16H2O (3) with a mixture of 2,2′- and 4,4′-bpy have been characterized, and a coordination polymer with polyoxometalate guests Na3[4,4′-Hbpy]{Cu4(4,4′-bpy)8(H2O)8}[PW11CuO39(H2O)][PW10Cu2O38(H2O)2]·38H2O (4) with 4,4′-bpy has been obtained. Finally, in basic medium (pH = 10) the unprecedented molecular cluster Na2[{Cu8(2,2′-bpy)8}(PW8O31)2]·15H2O (5) has been evidenced. Magnetic studies of compound 2 revealed that the predominant interactions involve only 4 paramagnetic centers, which are interacting within pairs, among the 6 Cu(II) centers. The χMT
=
f(T) curve can be fitted using the dinuclear expression appropriate to the HDVV isotropic exchange Hamiltonian H
=
−JS1×S2, with S1
=
S2
=
½ and J
=
−105.4 cm−1, showing strong antiferromagnetic interactions within the two Cu(II) pairs.