The present invention relates to a process for the recovery and refining of rhodium starting from a mixture containing rhodium and other transition metals, including those of the platinum Group, as well as metals of the main Groups, said process comprising the following passages: a) formation of an adduct between rhodium trichloride and a halide of a metal selected from metals of Groups IIA, IIIA, IVA, IVB, VB and VIB; b) carbonylation of the precipitated adduct, deriving from passage a) with the formation of rhodium halogen carbonyls and c) sublimation of the carbonylated product obtained in the previous passage. The main advantage of the above process consists in the production of an extremely pure product, with excellent yields.