The reaction of the tetrahedral diphosphorus complex [Cp2Cr2(CO)(4)(eta(2)-P-2)] (Cp = C5H5) (2) with Ag[Al{OC(CF3)(3)}(4)] (AgTEF) (3) leads to the formation of the Ag-I dimer [Ag-2(eta(2)-2) (eta(1)-2)(eta(1):eta(1)-2)(2)][TEF](2) (5). This dimer can be used as a suitable precursor for the synthesis of the unprecedented 1D organometallic-organic hybrid polymer [Ag-2(eta(1)-2)(2)(mu,eta(1):eta(1)-2)(2){mu,eta(1):eta(1)-(C8H4N2)}](n)[TEF](2n) (8) upon its reaction with 1,4-dicyanobenzene (7). The driving force for this supramolecular assembly reaction is supported by DFT calculations