The cluster [Os3(PMe)(C6H4)(CO)9] (1) reacts with phosphorus(III) ligands L [PEt3, PCy3, or P(OMe)3] to give the substitution products [Os3(PMe)(C6H4)(CO)9-xLx], clusters 2 (x = 1) and 3 (x = 2). The crystal structures of 1 and 2 (L = PEt3) are compared with that previously reported for [Os3(PEt)(C6H4)(CO)9]; each has two OsOs bonds and one non-bonding Os ··· Os distance (3.982(1), 4.014(1), and 4.008(2) Å, respectively, for the three compounds). A μ3-PMe or PEt group caps one face of the Os3 triangle and the opposite one is capped by a μ3-C6H4 ligand coordinated through σ-OsC bonds to two mutually bonded Os atoms and does not span the open Os ··· Os edge by σ-bonds as in other cases such as [Os3H(AsMe2)(C6H4)(CO)9]. Bonding to the third Os atom through one carbon atom involves π-orbitals predominantly, and there is evidence against an alkylidene component in the bridging such as was considered previously. The C6H4 ligand is rapidly mobile in 1, and in one of the two isomers of 2 with the ligand L at the central Os atom. The fluxionality is substantially suppressed when L is coordinated at a terminal Os atom as in the isomer of [Os3(PMe)(C6H4)(CO)8(PEt3)] whose structure was established crystallographically. The movement of the non-bonded Os ··· Os edge around the metal triangle does occur, but is slow.