The reactions of the P₂ ligand complex [Cp₂Mo₂(CO)₄(η²-P₂)] (Cp = C₅H₅, 1) with Ag[Al{OC(CF₃)₃}₄] (Ag[TEF]) in the presence of the rigid bipyridyl linkers 1,2-di(pyridin-4-yl)ethyne (3), 4,4′-bis(pyridin-4-ylethynyl)-1,1′-biphenyl (4) and 4,4′-bipyridine (5) possessing various lengths are studied. The reaction with the longer linkers (3 and 4) leads to the formation of the 1D organometallic–organic hybrid polymers [{Cp₂Mo₂(CO)₄(μ₄,η¹˸¹˸²˸²-P₂)}₂{Cp₂Mo₂(CO)₄(μ₃,η¹˸²˸²-P₂)}₂(μ,η¹˸¹-C₁₂H₈N₂)Ag₂]n[TEF]₂n (6) and [{Cp₂Mo₂(CO)₄(μ₄,η¹˸¹˸²˸²-P₂)}₂{Cp₂Mo₂(CO)₄(μ₃,η¹˸²˸²-P₂)}₂(μ,η¹˸¹-C₂₆H₁₆N₂)Ag₂]n[TEF]₂n (7) in high selectivity. A similar reaction with the short linker 5 affords a mixture of the 2D hybrid polymers [{Cp₂Mo₂(CO)₄(μ₄,η¹˸²˸²˸²-P₂)}₂(μ,η¹˸¹-C₁₃H₁₄N₂)Ag₂]n[TEF]₂n (8) and the 3D hybrid network [{Cp₂Mo₂(CO)₄(μ₄,η¹˸¹˸²:²-P₂)}₂(μ,η¹˸¹-C10H8N₂)Ag]n[TEF]₂n (9). However, a selective synthesis of 8 or 9 is possible when the reaction is performed at 0 °C and 60 °C, respectively.