Some intrinsically chiral [Rh6(CO)14(μ,κ2-PX)] clusters have been synthesized, beginning with reactions of [Rh6(CO)16−x(NCMe)x] (x = 1, 2) with PX, where PX represents the bidentate bridging ligands diphenyl(benzothienyl)phosphine (1), diphenyl(2-thienyl)phosphine (2), di(2-thienyl)phenylphosphine (3), tris(2-thienyl)phosphine (4), diphenyl(2-pyridyl)phosphine (5) and diphenylvinylphosphine (6). The ligand tris(2-furyl)phosphine (7) shows no bridging capability. When x = 1 the initial products are the clusters [Rh6(CO)15(κ1-PX)] which undergo spontaneous CO loss to form [Rh6(CO)14(μ,κ2-PX)]. The structures of the [Rh6(CO)15(κ1-PX)] clusters have been elucidated by IR, NMR spectroscopy and FAB-MS spectrometry, and have been found to involve phosphorus atom coordination to a rhodium atom. In addition, the solid state structures of the [Rh6(CO)14(μ,κ2-Ph2P(2-benzothienyl))] (8), [Rh6(CO)14(μ,κ2-Ph2P(2-thienyl))] (9), [Rh6(CO)14(μ,κ2-PhP(2-thienyl)2)] (10) and [Rh6(CO)14(μ,κ2-Ph2P(pyridyl))] (12) clusters have been determined by X-ray crystallography. The various types of chirality exhibited by these clusters are discussed. A simple model is proposed to account for the ratios of stereochemical isomers found in the Rh6(CO)14(μ,κ2-PhP(2-thienyl)2 cluster. The kinetics of formation of the bridged clusters from the monosubstituted [Rh6(CO)15(κ1-PX)] clusters have been studied.