The reaction of the organometallic diarsene complex [Cp2Mo2(CO)(4)(eta(2)-As-2)] (1) with Ag[Al{OC(CF3)(3)}(4)] (Ag[TEF]) yielded the Ag-I monomer [Ag(eta(2)-1)(3)][TEF] (2). This compound exhibits dynamic behavior in solution, which allows directed selective synthesis of unprecedented organometallic-organic hybrid assemblies upon its reaction with N-donor organic molecules by a stepwise pathway, which is supported by DFT calculations. Accordingly, the reaction of 2 with 2,2 '-bipyrimidine (L1) yielded the dicationic molecular compound [{(eta(2)-1)(2)Ag}(2)(mu-L1)][TEF](2) (3) or the 1D polymer [{(eta(2)-1)Ag}(mu-L1)](n)[TEF](n) (4) depending on the ratio of the reactants. However, its reactions with the pyridine-based linkers 4,4 '-bipyridine (L2), 1,2-bis(4-pyridyl)ethylene (L3) and 1,2-bis(4-pyridyl)ethyne (L4) allowed the formation of the 2D polymers [{(eta(2)-1)Ag}(2)(mu-Lx)(3)](n)[TEF](2n) [Lx=L2 (5), L3 (6), L4 (7), respectively]. Additionally, this concept was extended to step-by-step one-pot reactions of 1, [Ag(CH3CN)(3)][Al{OC(CF3)(2)(CCl3)}(4)] ([Ag(CH3CN)(3)][TEFCl]) and linkers L2-L4 to produce the 2D polymers [{(eta(2)-1)Ag}(2)(mu,Lx)(3)](n)[TEFCl](2n) [Lx=L2 (8), L3 (9), L4 (10), respectively].