One new conjugated symmetric fulvene ligand L1 and two new unsymmetric fulvene ligands L2 and L3 were synthesized. Five new supramolecular complexes, namely Ag2(L1)3(SO3CF3)3 (1) (1, monoclinic, P21/c; a=12.702(3) Å, b=26.118(7) Å, c=13.998(4) Å, β=96.063(4)°, Z=4), [Ag(L1)]ClO4 (2) (monoclinic, C2/c; a=17.363(2) Å, b=13.2794(18) Å, c=13.4884(18) Å, β=100.292(2)°, Z=8), [Ag(L1)(C6H6)SbF6]β0.5C6H6βH2O (3) (monoclinic, P21/c; a=6.8839(11) Å, b=20.242(3) Å, c=18.934(3) Å, β=91.994(3)°, Z=4), Ag(L2)(SO3CF3) (4) (triclinic, P1h; a=8.629(3) Å, b=10.915(3) Å, c=11.178(3) Å,R)100.978(4)°, β=91.994(3)°, ç=105.652(4)°, Z=2), and Ag(L3)(H2O)(SO3CF3) (5) (triclinic, P1h; a=8.914(5) Å, b=10.809(6) Å, c=11.283(6) Å, R )69.255(8)°, β=87.163(9)°, ç=84.993(8)°, Z=2) were obtained through self-assembly based on these three new fulvene ligands in a benzene/toluene mixed-solvent system. Compounds 1-5 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The results indicate that the coordination chemistry of new fulvene ligands is versatile. They can adopt either cis- or trans-conformation to bind soft acid Ag(I) ion through not only the terminal -CN and furan functional groups but also the fulvene carbon atoms into organometallic coordination polymers or discrete complexes. In addition, the luminescent properties of L1-L3 and their Ag(I) complexes were investigated preliminarily in EtOH and solid state.