The reaction of Rh-6(CO)(14)(Ph2PCH=CH2) with a twofold excess of GaCp* (Cp* = C5Me5) affords two novel heterometallic clusters Rh-6(CO)(13)(mu. kappa(3)-Ph2PC2H3)(mu(3)-GaCp*) (1) and Rh-6(CO)(13)(kappa(1)-Ph2PC2H3)(mu(3)-GaCp*)(2) (2) in a moderate yield. The hemilabile behavior of coordinated diphenylvinylphosphane in the starting cluster allows the easy insertion of GaCp* into the cluster coordination sphere, which eventually gives the cluster 1 with face-bridging coordination of the gallium fragment and the phosphane ligand recoordinated in an edge-bridging position. The further substitution of the vinyl function in 1 for the second GaCp* ligand affords cluster 2, where recoordination of the double bond is blocked by steric hindrance from adjacent GaCp* fragments. Both clusters were structurally characterized by X-ray crystallography in the solid state and by IR and NMR spectroscopy in solution. Hemildbility of diphenylvinylphosphane in 1 was independently confirmed by the cluster reaction with CO, which gives the Rh-6(CO)(14)(kappa(1)-Ph2PC2H3)(GaCp*) adduct (3) with the phosphane ligand only coordinated through the phosphorus atom. (c) Wiley-VCH Verlag GmbH & Co. KGaA.