Disclosed are dirhodium catalyst compositions. One such dirhodium catalyst composition includes a dirhodium catalyst and a solid support. The dirhodium catalyst includes a Rh—Rh moiety and four bridging ligand moieties. The dirhodium catalyst and the solid support are bound together, but they are not covalently bound together via one or more of the bridging ligand moieties. Another such dirhodium catalyst composition includes a dirhodium tetracarboxylate catalyst and a solid support, and the dirhodium tetracarboxylate catalyst and the solid support are bound together. Yet another such dirhodium catalyst composition includes a dirhodium catalyst and a solid support, where the dirhodium catalyst includes a Rh—Rh moiety and where the dirhodium catalyst and the solid support are bound together via at least one of the rhodiums' axial positions. The compositions can be used in a number of reactions, including insertion reactions (e.g., C—H insertions, Si—H insertions, O—H insertions, and N—H insertions), cyclopropanation reactions, annulations (e.g., [3+2] annulations and [3+4] annulations), and ,-diarylalkanoate synthesis. Methods for making the dirhodium catalyst compositions are also disclosed.