Two new fulvene ligands, L1 and L2, have been synthesized by an aroylation reaction of the cyclopentadienyl anion. The coordination chemistry of L1 and L2 was investigated. Two novel CpAg(I)-containing polymeric compounds, 1 ([Ag4(L1)2(í-H2O)2(SO3CF3)4]β(í-bis-è1-C6H6))βH2O) and 2 ([Ag2(L2)(H2O)(SO3CF3)2]β0.5(C6H6)), have been synthesized. Compounds 1 and 2 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The solid state structure of 1 features a macro-ring-containing one-dimensional chain motif. The solid state structure of 2 features a one-dimensional doublechain motif. These double chains are further cross-linked to each other via CpAg(SO3CF3)2-AgCp (AgβββAg contact of 4.215(15) Å) linkage into a novel 2-D network with large cavities (effective cross-section of ca. 21 9 Å), in which the benzene guest molecules are located.