The reaction of the diphosphorus complex [Cp2Mo2(CO)(4)((2)-P-2)] (1), with the Cu-I salts [Cu(CH3CN)(4)][BF4] or [Cu(CH3CN)(4)][PF6], and a mixture of [Cu(CH3CN)(4)][BF4] and CuCl in the presence of 2,2-bipyrimidine (2) is studied. Depending on the Cu-I salts used and the layering solvent involved in the crystallisation, a variety of novel coordination compounds are accessible in moderate to excellent yields (26-80%): the novel dicationic molecular organometallic-organic hybrid complexes [{Cp2Mo2(CO)(4)(mu(3),(1:2:2)-P-2)}(4)(mu(2),(1:1:1:1)-C8H6N4)Cu-2][BF4](2) (3) and [{Cp2Mo2(CO)(4)(mu(3),(1:2:2)-P-2)}(2){Cp2Mo2(CO)(4)(mu(3),(2:2:2)-P-2)}(2)(mu(2),(1:1:1:1)-C8H6N4)Cu-2][PF6](2) (4), the unique neutral 1D organometallic-organic hybrid polymer [{Cp2Mo2(CO)(4)(mu(4),(1:1:2:2)-P-2)}(2)(mu(2),(1:1:1:1)-C8N6N4)(CuCl)(2)](n) (5) and the unprecedented 2D organometallic-organic hybrid polymer [{Cp2Mo2(CO)(4)(mu(4),(1:1:2:2)-P-2)}(mu(2),(1:1:1:1)-C8H6N4){Cu-2(mu-Cl)}](2)[BF4](2n) (6).