Three new organic–inorganic hybrid materials with 4,4′-bipy ligands and copper cations as linkers, [Cu II(H 2O)(4,4′-bipy) 2][Cu II(H 2O)(4,4′-bpy) 2] 2H[Cu IIP 8Mo 12O 62H 12] · 5H 2O ( 1), [Cu I(4,4′-bipy)][Cu II(4,4′-bipy)] 2 (BW 12O 40) · (4,4′-bipy) · 2H 2O ( 2) and [Cu I (4,4′-bipy)] 3 (PMo 12O 40) · (pip) · 2H 2O ( 3) (pip = piperazine; 4,4′-bipy = 4,4′-bipyridine), have been hydrothermally synthesized. The single X-ray structural analysis reveals that the structure of 1 is constructed from [Cu(H 2O)(4,4′-bipy) 2] complexes into a novel, three-dimensional supermolecular network with 1-D channels in which Cu[P 4Mo 6] 2 dimer clusters reside. To the best of our knowledge, compound 1 is the first complex in which the [P 4Mo 6] clusters have been used as a non-coordinating anionic template for the construction of a novel, three-dimensional supermolecular network. Compound 2 is constructed from the six-supported [BW 12O 40] 5− polyoxoanions and [Cu I(4,4′-bipy)] and [Cu II(4,4′-bipy)] groups into a novel, 3-D network. Compound 3 exhibits unusual 3-D supramolecular frameworks, which are constructed from tetrasupporting [PMo 12O 40] 3− clusters and [Cu I (4,4′-bipy) n ] coordination polymer chains. The electrochemical properties of 2 and 3 have been investigated in detail.