Four hybrid inorganic - metalorganic compounds containing copper(II)-monosubstituted Keggin polyoxotungstates, K-3[Cu-I(4,4 '-bpy)](3)[(SiW11CuO39)-O-II] center dot 11H(2)O (1), (paraquat)(3)[(SiW11CuO39)-O-II], 6H(2)O (2; paraquat = N, N '-dimethyl-4,4 '-bipyridinium), K-3[Cu-I(4,4 '-bpy)](3)[(GeW11CuO39)-O-II] center dot 11H(2)O (3), and Na-2[Cu-I(4,4 '-bpy)](3)[(PW11CuO39)-O-II(H2O)] center dot 4H(2)O (4), have been synthesized under autogenous pressure hydrothermal conditions and characterized by elemental analysis and infrared spectroscopy (FT-IR). The crystal structures of 1, 2, and 4 have been established by single-crystal X- ray diffraction. The crystal packings are characterized by the presence of monodimensional extended entities: either the polymeric polyanion [SiW11CuO39](n)(6n-) (2), the cationic [Cu(4,4 '-bpy)](n)(n+) chain (4), or both simultaneously as in compound 1, where the inorganic and metalorganic sublattices are mutually perpendicular. To asses the influence of packing in the copper(I) complex structural diversity found in compounds 1 and 4, a search in the CSD database has been performed and the resulting geometrical features have been analyzed and compared with experimental crystallographic data and DFT calculations.