Tris(allyl)rhodium(III) reacts with the hydroxyl-terminated surfaces of silica, titania, and alumina to form a surface bis(allyl)rhodium(III) fragment. In the presence of CO, this supported organometallic fragment undergoes a series of reactions which model elementary steps of heterogeneous C-C and C-O bond formation. On surfaces with low proton content (silica-400, alumina, titania), 1,5-hexadiene is produced quantitatively by reductive coupling of two allyl ligands, with simultaneous formation of surface-Bound dicarbonylrhodium(I). In the presence of a high concentration of surface protons (silica-200), there are two reaction pathways : (i) formation of propene by reaction of an allyl ligand with a surface proton and (ii) insertion of CO into the metal-carbon bond to give the acyl complex CH2=CHCH2C(O)Rh(III), detected by IR. The acyl ligand may undergo reductive elimination with an allyl ligand, giving the minor product 1,6-heptadien-4-one, or with a siloxy ligand, with transfer of 3-butenoate to the silica support (extracted as methyl-3 butenoate). The dicarbonylrhodium(I) product is mobile on the surface of silica : dimerization occurs spontaneously. Under H-2, reduction and aggregation of the dimers leads to small metal particles.