The reaction of Rh6(CO)14(Ph2PCH=CH 2) with a twofold excess of GaCp* (Cp* = C 5Me5) affords two novel heterometallic clusters Rh 6(CO)13(μ,κ3-Ph2PC 2H3)(μ3-GaCp*) (1) and Rh 6(CO)13(κ1-Ph2PC 2H3)(μ3-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. Hemilability of diphenylvinylphosphane in 1 was independently confirmed by the cluster reaction with CO, which gives the Rh6(CO)14(κ1-