The reaction of the lacunary polyoxometalate precursor Na-9[B-alpha-BiW9O33]center dot 19 center dot 5H(2)O with Cu(II) ions was explored in search of new economic ways to copper. tungstobismuthates as interesting prototypes for water oxidation and reduction catalysts. The emerging series of new 0D-3D polyoxometalate architectures with distinct copper cores was structurally characterized. Na6Rb6[Cu-3-(H2O)(3)(BiW9O33)(2)] (Cu-4) and 3D-K6.56Cu0.43H2.(20)[(Cu3Cl)-(K-2 (62) Cu-0.38(H2O)(3))(B-alpha-BiW9O33)(2)}center dot 13H(2)O (Cu-5) display a Cu-3(H2O)(3) core. The 2D representatives Na-12[Cu-2(H2O)(4)-Cl-2(BiW10O35)(2)] (Cu-1a), Na-10[Cu-2(H2O)(6)(BiW10O35)(2)] (Cu-1b), 2D-Na7K3Cu0.5Cl[Cu-2(H2O)(4)(BiW10O35)(2)] (Cu-2), and 2D-Na5.5K2.5Cu[Cu-2(H2O)(4)(BiW10O35)(2)] (Cu-3) contain Cu-2(H2O)(n)W2O4 cores. Interestingly, the bismuth-free 1D paratungstate B Na4K4Cu[H2W12O42] (Cu-6) is formed through reassembly of the precursor. Cu-5 displays a disordered transition metal core, implying the presence of the polyanions [Cu-4(H2O)(4)(BiW9O33)(2)}(10-) and [Cu-5(H2O)(5)(BiW9O33)(2)](8-). The magnetic properties of Cu-5 as well as its activity as visible light-driven H-2 and O-2 evolution catalyst were evaluated.