Rhodium complexes have found a wide application in the catalytic C-C bond activation of various substrates depending on the ligand environment. The reaction proceeds with strained carbocycles (cyclopropanes, cyclobutanes and their derivatives), with non-strained C-C bonds activated by carbonyl or other functionalities, or it can result in decarbonylation (aldehydes, acyl halides etc.). Rhodium catalyzed C-C bond cleavage reactions were also used as key steps in syntheses of several natural compounds or biologically active molecules.