For the first time, the tetrahedral diphosphorus complex [Cp2W2(CO)(4)(mu,eta(2):eta(2)-P-2)] (Cp = C5H5) (3) is used as a connecter in supramolecular chemistry. The treatment of 3 with Cu-I halides leads to the formation of the new one-dimensional (1D) linear polymers [Cu(mu-X){Cp2W2(CO)(4)(mu,eta(2):eta(2):eta(1):eta(1)-P-2)}](n) {X = Cl (4), Br (5), I (6)}. The coordination polymers (CPs) 4-6 are almost insoluble in organic solvents, thus, their P-31 MAS-NMR spectra were recorded and found to be remarkably influenced by their solid-state structures. Additionally, we demonstrate that by reacting the Cp-substituted diphosphorus complex [Cp ' W-2(2)(CO)(4)(mu,eta(2):eta(2)-P-2)] {Cp ' = C5H4{C(CH3)(3)}} (7) with CuBr, the unprecedented soluble 1D CP [Cu(mu-Br){Cp ' W-2(2)(CO)(4)(mu,eta(2):eta(2):eta(1):eta(1)-P-2)}](n) (8) is obtained. Furthermore, the reactions of 3 with the Ag-I salts Ag[CF3SO3] and Ag[PF6] result in the formation of the oligomeric dicationic species [Ag-2{Cp2W2(CO)(4)(mu,eta(2):eta(2):eta(2)-P-2)}(2) {Cp2W2(CO)(4)(mu,eta(2):eta(2):eta(1):eta(1)-P-2)}(2)][X '](2) {X ' = [CF3SO3](-) (9), [PF6](-) (10)}.