The subjects of the invention are new heterogenized rhodium complexes, the methods of their synthesis and their application as catalysts for synthesis of organosilicon compounds by hydrosilylation. The subject of the invention are new siloxide rhodium(I) complexes immobilised on the silica surface, of the general formula 1. [(≡SiO)(L)Rh(diene)] The second subject of the invention is the method of synthesis of the new rhodium complexes of the general formula 1. The third subject of the invention is the method of obtaining the organosilicon compounds in the reaction of hydrosilylation between the selected alkenes or functionalised alkenes containing the terminal C═C bond and the appropriate compounds containing the Si═H bond selected from silanes, (poly)siloxanes and (poly)carbosiloxanes, in the presence of heterogenized rhodium catalysts, of the general formula 1.