A series of highly flexible bis-phospholane ligands 3a-g with 5-11 methylene groups in the backbone was synthesized and fully characterized by mass spectrometry and NMR (H-1, C-13, P-31) and IR spectroscopy. Gold bis-phospholane macrocydes containing 16 ([Au2Cl2(mu-3a)(2)],4), 20 ([Au2Cl2(mu-3c)(2)], 5), 24 ([Au2Cl(mu-3e)(2)]Cl, 6), and 28 ([Au2Cl2(mu-3g)(2)], 7) atoms in the ring were obtained in one step from [AuCl(tht)] (tht = tetrahydrothiophene) and 3a,c,e,g in excellent yield. In addition, three polymers resulting from aurophilic interactions, i.e., zigzag chains in [Au2Cl2(mu-3b)]. (8) and nanotubes in [Au2Cl2(mu-3d)](x) (9) and [Au2Cl2(mu-3f)](x) (10), with Au center dot center dot center dot Au distances of 309.41(2), 330.24(6), and 335.82(3) pm, respectively, were obtained. Halide abstraction of 4-7 with AgBF4 led to macrocydes [Au-2(mu-3a)(2)](BF4)(2) (11), [Au-2(mu-3c)(2)](BF4)(2) (12), [Au-2(mu-3e)(2)](BF4)(2) (13), and [Au-2(mu-3g)(2)](BF4)(2) (14). In 12., the monomers are connected by strong aurophilic interactions (Au center dot center dot center dot Au 296.57(1) pm) in the solid state with formation of a polymeric chain. All complexes were fully characterized by NMR (H-1, C-13, P-31) and IR spectroscopy, mass spectrometry, and X-ray diffraction.