A series of new rigid distibines, 1,8-bis(R2Sb)naphthalene (R = Me: (1); R = Ph: (2)), and chiral distibines, 2,2′-bis(R2Sb)-1,1′-binaphthyl (R = Me: (3); R = Ph: (4) obtained as racemic mixtures) and the discrete enantiomers of 4,5-bis((R2Sb)methyl)-2,2-dimethyl-1,3-D/L-dioxolane (R = Me: (5) (L), (7) (D); R = Ph: (6) (L), (8) (D)) have been obtained in high yields, using either electrophilic halostibine reagents with di-lithium reagents ((1)–(4)) or nucleophilic stibide reagents with dibromo-derivatives ((5)–(8)). The distorted octahedral complexes [Mo(CO)4(L)], L = (1)–(8), planar [PtCl2(L)], L = (1), (2), (3), (5), and neutral, five-coordinate [RhCl(cod)(L)], L = (2), (4), (6), are reported and trends in the spectroscopic data are discussed in terms of the ligand donor properties. Crystal structures of (3) and [Mo(CO)4(3)] reveal significant structural changes occur upon coordination, and these are also reflected in the solution NMR spectroscopic parameters. Changes in the C–Sb–C angles and C–Sb bond distances upon coordination of (3) are discussed in term of increased s/p orbital mixing. Air oxidation of (1) forms a very unusual stibine oxide, the structure of which shows a distorted Sb4O4 cubane core (bridging O atoms) with two orthogonal naphthalene units.