The rhodium catalyst is a suitable promoter, used to activate carbon-hydrogen(C-H) bonds, and has emerged as a challenging and attractive tool for catalysis. Rhodium catalysis finds increasing interest in the catalytic dehydrogenative cross-coupling, allowing elegant C-C bond construction. Although palladium has been the metal of choice for most examples, Rh catalysts can also be suitable promoters for this activation. Additionally, rhodium provides access to important couplings, such as aryl-aryl, aryl-alkene, and alkene-alkene, as viable routes to valuable organic frameworks.